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02
Vibrationallyresolved electronic spectra in GAUSSIAN 09
V. Barone, J. Bloino, M. Biczysko
Scuola Normale Superiore, Piazza dei Cavalieri, 7 I56126 Pisa, Italy
General overview
In a ﬁrst approximation level, electronic spectra (UVvis, photoelectron, Xray, etc.) can be simulated by computing
vertical excitation energies at geometrical structures optimized for the ground electronic state, with the resulting stick
spectra subsequently convoluted by Gaussian or Lorentzian functions. However, such a treatment neglects completely
dynamic effects, which inﬂuence signiﬁcantly the spectrum lineshape in many cases. To overcome this limitation,
a new procedure to compute vibrationallyresolved electronic spectra has been included in GAUSSIAN. It relies on
the FranckCondon principle [1, 2] to evaluate the intensities of transitions between two vibronic states. This is done
by considering that the nuclear positions are mostly unaltered by the electron jump which takes place during the
electronic transition.
Figure 1: Convergence of the phosphoresence spec
trum for chlorophyll c2 with different maximum
number of integrals to compute (N
I
) for each class.
To deal with mediumtolarge systems, an efﬁcient pre
screening scheme [3, 4] is used to choose the most relevant
transitions. It is designed to be fast and simple enough to have
little incidence on the computational cost of the spectrum gen
eration, while providing an accurate choice of the transitions to
deal with in order to produce accurate spectra. One of its main
features is that it relies on the number of integrals to compute
and not on the dimensionality of the system. As a consequence,
GAUSSIAN can be tailored to perform fast calculations while
retaining the general shape of the spectrum at ﬁrst, as shown on
ﬁgure 1. It is noteworthy that this prescreening scheme works
as a blackbox procedure and performs a full dimensional treat
ment, considering all vibrational modes of the studied system.
Additionally, GAUSSIAN accepts a wide range of settings to
adjust the calculations or to modify the layout of the spectrum
when needed. Because calculations to generate the theoretical
spectrum are independent on the lower and upper bound of the latter, the energy range on which the simulation is
performed has a very little impact on the computational costs
1
1
However, a high resolution, given by a small interval between two measuring points of the discretized spectrum, associated to a broad band
can noticeably slow down the calculations.
1
Contents
1 Introduction 2
2 Theoretical background 2
3 Quick start 10
4 List of options 13
5 Some practical examples 17
6 Description of the errors reported by GAUSSIAN 18
1 Introduction
In this new release of GAUSSIAN, it is possible to compute vibrationallyresolved absorption and emission spectra.
This white paper aims at introducing the general theory underlying such calculations and presenting the possibilities
offered to generate electronic spectra inside GAUSSIAN.
The document is divided as follows. After a brief introduction of the basic theory used in GAUSSIAN to generate
vibronic spectra, a quick presentation of its basic usage is given. The main features of the input and output will then
be described. The second part of the document is devoted to more advanced cases and to the tools to control and
ﬁnetune the calculations to meet speciﬁc needs. The available options and their purpose will be listed, followed by
examples of applications showing the usage of the most common ones. The last part summarizes the most common
errors reported by GAUSSIAN and possible workarounds. This section is not aimed at being exhaustive and alternative
solutions can work as well or even be more adapted to some particular cases.
The following typographic conventions will be used thereafter:
•
′
: placed next to a letter/symbol, refers to the initial state
•
′′
: placed next to a letter/symbol, refers to the ﬁnal state
• N
A
: represents the number of atoms in the molecule or system of interest
• N: represents the number of normal modes in the molecule or system of interest
• M: designates a matrix or vector
• M
i
or M(i): represents the ith element of vector M
• M
ij
or M(i, j): represents the i, j element of matrix M
Note: For convenience, the notation adopted in this document is slightly different from the spectroscopic conventions
since the relative energies of the initial and ﬁnal states are not taken into account when using
′
and
′′
. This allows to
treat indifferently the similar cases of absorption and emission without duplicating the formulae.
2 Theoretical background
The theoretical description in this section is not intended to be exhaustive but rather to give a sufﬁcient background in
order to use GAUSSIAN for the simulation of vibrationally resolved electronic spectra. It is divided in three subsec
tions. The ﬁrst one presents a general theoretical background and the approximations used to compute the transition
dipole moment and the transition intensities. This will help to understand the possibilities given by the FranckCondon
principle as well as the limit of such a method. The second part deals with the prescreening method used by GAUS
SIAN to choose a priori the most intense transitions. The parameters on which it relies as well as their inﬂuence are
described there. Finally, a discussion on the guessing of spectrum convergence is carried out.
2
Calculation of the transition dipole moment
Line intensities in onephoton absorption and emission spectra depend on the square of the transition dipole moment
Ψ
′
 µ  Ψ
′′
as well as on the radiation frequency (ω)
2
:
σ(ω)
abs
=
4π
2
ω
3c
¸
′
ρ
′
¸
′′
Ψ
′
 µ  Ψ
′′
2
δ(E
′′
−E
′
−¯hω) (1)
σ(ω)
emi
=
4ω
3
3¯ hc
3
¸
′
ρ
′
¸
′′
Ψ
′
 µ  Ψ
′′
2
δ(E
′′
−E
′
+ ¯ hω) (2)
where ρ
′
is the Boltzmann population of each initial state and σ(ω) is the rate of photon absorption (or emission) per
molecule and per unit of radiant energy. Ψ
′
and Ψ
′′
represent the molecular wave functions of the initial and ﬁnal
state, respectively.
In the frame of the BornOppenheimer approximation, it is possible to write the molecular wave function Ψ as a
product of an electronic wave function ψ
e
and a nuclear wave function ψ
n
. The transition dipole moment can then be
written,
Ψ
′
 µ  Ψ
′′
= ψ
′
e
ψ
′
n
 µ
e
 ψ
′′
e
ψ
′′
n
+ ψ
′
e
ψ
′
n
 µ
n
 ψ
′′
e
ψ
′′
n
(3)
Since the electronic wave functions are orthogonal to each other, the second term of the rhs in the previous equation
vanishes.
We further assume that the Eckart conditions [5] are met, so that the nuclear wave function can be, with a good ap
proximation, separated into a rotation and a vibrational contribution, the translational part being completely separated
from the other two and discarded here. In the treatment presented here, rotational energies are considered sufﬁciently
small and will not be taken into account.
Using both approximations, the transition dipole moment can ﬁnally be written,
Ψ
′
 µ  Ψ
′′
≈ ψ
′
v
 µ
if
 ψ
′′
v
(4)
where µ
if
= ψ
′
e
 µ  ψ
′′
e
is the electronic transition dipole moment.
In the method implemented in GAUSSIAN, the harmonic approximation is also used. As a consequence, it is
possible to write the multidimensional vibrational wave function ψ
v
as a product of monodimensional wave functions
ψ
v
i
(Q
i
), where Q
i
is one of the N normal coordinates, describing the ith vibration of the molecule.
However, since the analytic form of the electronic transition dipole moment is unknown, these approximations are
not yet sufﬁcient to compute the transition dipole moment. An additional approximation is done by using the Franck
Condon principle, proposed by Franck [1] and mathematically formalized by Condon [2]. The underlying theory is
that, during a transition, the electron jump in a molecule takes place in such a short time that the relative positions
and velocities of the nuclei are nearly unaltered by the molecular vibrations. Following this principle, schematically
shown in ﬁgure 2, the most intense transition will be from the chosen initial state to a ﬁnal state being at a minimum
of the lowest potential surface vertically upward. Since this approximation is very restrictive by assuming that the
electronic transition dipole moment remains constant during the transition, a more ﬂexible approach is adopted here.
Indeed, since the shifts of the nuclear positions in the molecule are often fairly small during the electronic transition,
it is possible, with a good accuracy, to develop the electronic transition dipole moment in a Taylor series about the
equilibrium geometry of one state of reference, which is the ﬁnal state in our case:
µ
if
(Q
′′
) ≃ µ
if
(Q
′′
0
) +
N
¸
k=1
∂µ
if
∂Q
′′
k
0
Q
′′
k
+
1
2
N
¸
k=1
N
¸
l=1
∂
2
µ
if
∂Q
′′
k
∂Q
′′
l
0
Q
′′
k
Q
′′
l
+ . . . (5)
where Q
′′
0
represents the equilibrium geometry of the ﬁnal state.
2
With respect to the formulae presented here, GAUSSIAN does not take into account the constant part to calculate the intensity of the
spectrum lines
3
Figure 2: The FranckCondon prin
ciple is shown by the vertical dotted
line. Following this principle, the high
est probability of transition corresponds
to 0
′
 2
′′
where the overlap of the
wave functions is the highest.
The zeroth order term corresponds to a static electronic transition dipole. This
is a direct application of the FranckCondon principle mentioned above. As a con
sequence, it is referred as the FranckCondon (FC) approximation. When dealing
with fullyallowed transitions (µ
if
(Q
′′
0
) ≫ 0), this approximation generally
gives very good results.
However, in the case of weaklyallowed (µ
if
(Q
′′
0
) ∼ 0) or dipoleforbidden
(µ
if
(Q
′′
0
) = 0) electronic transitions, this approximation is not describing
correctly the overall spectrum, missing the most intense vibronic transitions. It is
necessary to consider a variation of the dipole moment during the transition. A
ﬁrst approximation is to account for a linear variation of the dipole moment with
the normal coordinates. This corresponds to the ﬁrst order of the Taylor expansion
and is referred as the HerzbergTeller [6] (HT) approximation
3
. Hereafter, the FC
approximation considers only the ﬁrst term in the rhs of eq. 5, HT the second one,
and FCHT both terms, as approximation of µ
if
.
Using eq. 5, the transition dipole moment can be written:
Ψ
′
 µ  Ψ
′′
= µ
if
(Q
′′
0
) ψ
′
v
 ψ
′′
v
+
N
¸
k=1
∂µ
if
∂Q
′′
k
0
ψ
′
v
 Q
′′
k
 ψ
′′
v
+
1
2
N
¸
k=1
N
¸
l=1
∂
2
µ
if
∂Q
′′
k
∂Q
′′
l
0
ψ
′
v
 Q
′′
k
Q
′′
l
 ψ
′′
v
(6)
The overlap integral ψ
′
v
 ψ
′′
v
is also referred to as the FranckCondon inte
gral. The integrals in the second and third terms of equation 5 depend on the normal coordinates and therefore cannot
be, in this form, generalized to any problem. To simplify the calculation of the integrals given in equation 6, it is
necessary to transform them in more versatile and usable FranckCondon integrals. This is done by using the creation
and annihilation operators from the second quantization, respectively a
†
i
and a
i
, deﬁned as
a
†
i
=
ω
i
2¯ h
Q
i
−
d
dQ
i
(7)
a
i
=
ω
i
2¯ h
Q
i
+
d
dQ
i
(8)
Hence,
Q
i
=
¯h
2ω
i
1/2
a
i
+ a
†
i
(9)
In the current implementation, the Taylor expansion of the electronic transition dipole moment is supported up to
the second term in the rhs in eq. 5. As a consequence, the approximation of µ
if
will be limited to the FranckCondon
and HerzbergTeller terms. In addition, the vibrational wave function wil be replaced from now on by a vector “v”
containing the quantum numbers v
i
representing the same vibrational state described by ψ
v
:
 v =  ψ
v
= 
N
¸
i=1
ψ
v
i
Using eq. 9, the second term integral in the rhs of eq. 6 can be rewritten,
v
′
 Q
′′
k
 v
′′
=
¯h
2ω
′′
k
v
′′
k
v
′
 v
′′
−1
′′
k
+
v
′′
k
+ 1 v
′
 v
′′
+ 1
′′
k
(10)
3
In their original work, Herzberg and Teller considered the initial state as the state of reference for the linear variation of the electronic
transition dipole moment. We use here a more general interpretation of their work by applying to any state of reference.
4
where  v
′′
+ 1
′′
i
represents, from the energy perspective, a vibrational state which differs from the state represented
by  v
′′
by the eigenvalue of the monodimensional Schr¨ odinger equation E
v
′′
i
+1
= ¯ hω
′′
i
(v
′′
i
+ 1/2) = E
v
′′
i
+ ¯ hω
′′
i
.
Inserting eq. 10 in eq. 6, it is possible to write the transition dipole moment integral as a combination of overlap
integrals:
Ψ
′
 µ  Ψ
′′
=µ
if
(Q
′′
0
) v
′
 v
′′
+
N
¸
k=1
∂µ
if
∂Q
′′
k
0
¯h
2ω
′′
k
v
′′
k
v
′
 v
′′
−1
′′
k
+
v
′′
k
+ 1 v
′
 v
′′
+ 1
′′
k
(11)
The overlap integrals are given by the equation,
v
′
 v
′′
= π
−N/2
det
Γ
′
Γ
′′
1/4
det(J)
1/2
N
¸
i=1
2
v
′
i
2
v
′′
i
(v
′
i
!)(v
′′
i
!)
−1/2
×
+∞
−∞
dQ
′′
1
. . . dQ
′′
N
N
¸
i=1
H
v
′
i
(Γ
′
i
1/2
Q
′
i
)H
v
′′
i
(Γ
′′
i
1/2
Q
′′
i
)
×exp
−
1
2
(Q
′
T
Γ
′
Q
′
+Q
′′
T
Γ
′′
Q
′′
)
(12)
where Γ
′
and Γ
′′
are the diagonal matrices of the reduced frequencies from the initial and ﬁnal states, respectively,
and H
v
i
(q
i
) is a Hermite polynomial of degree v
i
deﬁned by:
H
v
i
(q
i
) = (−1)
v
i
e
q
2
i
d
v
i
dq
v
i
i
e
−q
2
i
(13)
A ﬁrst issue to calculate the integral in eq. 12 arises from the fact that each vibrational wave function is expressed
in a different set of normal coordinates. To overcome this, the linear transformation proposed by Duschinsky [7] to
express the normal coordinates of one state with respect to the other’s is used,
Q
′
= JQ
′′
+K (14)
where J is called the Duschinsky matrix and represents the mixing of the normal modes during the transition, and K
is the shift vector due to the changes in geometry between the initial and ﬁnal states. This transformation is generally
a good approximation, when the molecule does not undergo a noticeable distortion during the transition.
The rotation or Duschinsky matrix and shift vector are given by:
J =
L
′
−1
L
′′
(15)
K =
L
′
−1
M
1/2
∆X (16)
where L
′
and L
′′
are the transformation matrices from massweighted Cartesian coordinates to normal coordinates,
Mis the diagonal matrix of atomic masses and ∆Xis a vector representing the shift of nuclear Cartesian coordinates
between the initial and ﬁnal states.
J and K can be printed in GAUSSIAN with the keyword PrtMat in the ReadFCHT section (with the respective
values 1 and 2 as shown in the keywords list).
In addition, while the overlap integral between the vibrational ground states 0
′
 0
′′
can be straightforwardly
calculated, this is generally not the case for v
′
 v
′′
where v
′
and/or v
′′
are not null. Among the several compu
tational approaches proposed till now, we have selected the Sharp and Rosenstock’s one [8]. However, their original
work was based on analytic formulae for each possible combination of v
′
and v
′′
and it is not adapted when dealing
with a large number of normal modes. A more versatile method based on recursive formulae [9], which follows a
similar formalism is described here.
5
First, two dummy vectors, T and U, are deﬁned to be nearnull so that,
H
v
′ (Γ
′
1/2
Q
′
) =
∂
v
′
∂T
v
′
exp
−T
2
+ 2T
T
Γ
′
1/2
Q
′
T=0
(17)
and
H
v
′′ (Γ
′′
1/2
Q
′′
) =
∂
v
′′
∂U
v
′′
exp
−U
2
+ 2U
T
Γ
′′
1/2
Q
′′
U=0
(18)
where
∂
v
′′
∂U
v
′′
=
∂
v
′′
1
∂U
v
′′
1
1
∂
v
′′
2
∂U
v
′′
2
2
. . .
∂
v
′′
N
∂U
v
′′
N
N
and
∂
v
′
∂T
v
′
=
∂
v
′
1
∂T
v
′
1
1
∂
v
′
2
∂T
v
′
2
2
. . .
∂
v
′
N
∂T
v
′
N
N
(19)
Replacing the Hermite polynomials in eq. 12 by their deﬁnitions given in eqs. 17 and 18, and using the Duschinsky
transformation, the following formula is obtained:
v
′
 v
′′
= π
−N/2
det
Γ
′
Γ
′′
1/4
det(J)
1/2
2
v
′
2
v
′′
v
′
!v
′′
!
−1/2
×
∂
v
′
∂T
v
′
∂
v
′′
∂U
v
′′
exp
−T
2
−U
2
dQ
′′
exp
1
2
Q
′′
T
J
T
Γ
′
JQ
′′
+Q
′′
T
J
T
Γ
′
K+K
T
Γ
′
JQ
′′
+K
T
Γ
′
K+Q
′′
T
Γ
′′
Q
′′
+ 2U
T
Γ
′′
1/2
Q
′′
+ 2T
T
Γ
′
1/2
JQ
′′
+ 2T
T
Γ
′
1/2
K
T=U=0
(20)
After developing and integrating the previous equation, we obtain:
v
′
 v
′′
=
2
v
′
2
v
′′
v
′
!v
′′
!
−1/2
∂
v
′
∂T
v
′
∂
v
′′
∂U
v
′′
2
N/2
det
Γ
′
Γ
′′
1/4
¸
det(J)
det
J
T
Γ
′
J +Γ
′′
1/2
×exp
−
1
2
K
T
Γ
′
K+
1
2
K
T
Γ
′
J(J
T
Γ
′
J +Γ
′′
)
−1
J
T
Γ
′
K
×exp
U
T
(2Γ
′′
1/2
(J
T
Γ
′
J +Γ
′′
)
−1
Γ
′′
1/2
−I)U
×exp
−2K
T
Γ
′
J(J
T
Γ
′
J +Γ
′′
)
−1
Γ
′′
1/2
U
×exp
T
T
(2Γ
′
1/2
J(J
T
Γ
′
J +Γ
′′
)
−1
J
T
Γ
′
1/2
−I)T
×exp
−2K
T
(Γ
′
J(J
T
Γ
′
J +Γ
′′
)
−1
J
T
−I)Γ
′
1/2
T
×exp
U
T
4Γ
′′
1/2
(J
T
Γ
′
J +Γ
′′
)
−1
J
T
Γ
′
1/2
T
(21)
To simplify the notation, 5 matrices referred to hereafter as Sharp and Rosenstock matrices are deﬁned:
A = 2Γ
′
1/2
J(J
T
Γ
′
J +Γ
′′
)
−1
J
T
Γ
′
1/2
−I
B = −2Γ
′
1/2
(J(J
T
Γ
′
J +Γ
′′
)
−1
J
T
Γ
′
−I)K
C = 2Γ
′′
1/2
(J
T
Γ
′
J +Γ
′′
)
−1
Γ
′′
1/2
−I
D = −2Γ
′′
1/2
(J
T
Γ
′
J +Γ
′′
)
−1
J
T
Γ
′
K
E = 4Γ
′′
1/2
(J
T
Γ
′
J +Γ
′′
)
−1
J
T
Γ
′
1/2
These matrices can also be printed in GAUSSIAN with the keyword PrtMat in the ReadFCHT section (with the
respective values 3, 4, 5, 6 and 7 as shown in the keywords list).
6
In addition, setting v
′
= v
′′
= 0, we obtain from eq. 21 the overlap integral between the vibrational ground
states:
0
′
 0
′′
= 2
N/2
det
Γ
′
Γ
′′
1/4
¸
det(J)
det
J
T
Γ
′
J +Γ
′′
1/2
×exp
−
1
2
K
T
Γ
′
K+
1
2
K
T
Γ
′
J(J
T
Γ
′
J +Γ
′′
)
−1
J
T
Γ
′
K
(22)
Hence, eq. 21 can be written,
v
′
 v
′′
=
2
v
′
2
v
′′
v
′
!v
′′
!
−1/2
∂
v
′
∂T
v
′
∂
v
′′
∂U
v
′′
0
′
 0
′′
×exp
U
T
CU+D
T
U+T
T
AT+B
T
T+U
T
ET
T=U=0
(23)
This equation is the starting point to generate two recursive formulae depending on the initial differentiation, with
respect to T
i
or U
i
. The procedure, using the Leibniz product rule, is to differentiate once by T
i
or U
i
and the result by
each T
j
and U
j
once, with j running from 1 to N. The procedure is straightforward so only the results are presented
here:
v
′
 v
′′
=
1
2v
′
i
B
i
v
′
−1
′
i
 v
′′
+
2(v
′
i
−1) A
ii
v
′
−2
′
i
 v
′′
+
N
¸
j=1
j=i
2v
′
j
A
ij
v
′
−1
′
i
−1
′
j
 v
′′
+
N
¸
j=1
v
′
j
2
E
ji
v
′
−1
′
i
 v
′′
−1
′′
j
(24)
and
v
′
 v
′′
=
1
2v
′′
i
D
i
v
′
 v
′′
−1
′′
i
+
2(v
′′
i
−1) C
ii
v
′
 v
′′
−2
′′
i
+
N
¸
j=1
j=i
2v
′′
j
C
ij
v
′
 v
′′
−1
′′
i
−1
′′
j
+
N
¸
j=1
v
′
j
2
E
ij
v
′
−1
′
j
 v
′′
−1
′′
i
(25)
with the ﬁrst equation corresponding to an initial differentiation by T
i
and the second one to U
i
.
In the current version in GAUSSIAN, all evaluated transitions start from the vibrational ground state of the initial
electronic state (T=0). As a consequence, only the last recursive equation is used without the last term in the righthand
side:
0
′
 v
′′
=
1
2v
′′
i
D
i
0
′
 v
′′
−1
′′
i
+
2(v
′′
i
−1) C
ii
0
′
 v
′′
−2
′′
i
+
N
¸
j=1
j=i
2v
′′
j
C
ij
0
′
 v
′′
−1
′′
i
−1
′′
j
(26)
A priori evaluation of the transition intensities
Using the recursive eqs. 24 and 25, it is possible to express any overlap integral v
′
 v
′′
with respect to 0
′
 0
′′
,
which is calculated exactly. Although, there is in principle an inﬁnite number of combinations to take into account,
most of them correspond to transtions of negligible intensity.
In GAUSSIAN, an a priori scheme [3, 4] selects the transitions which must be taken into account. This method
relies on a categorization of the latter with respect to the number of simultaneously excited modes in the ﬁnal state,
7
called classes. For instance, class 1 (C
1
) represents all transitions to ﬁnal vibrational states with a single excited mode
i, v
′
 0
′′
+v
′′
i
and class 0 contains the overlap integral between the vibrational ground states, 0
′
 0
′′
. Based on
this division, the overlap integrals in classes 1 and 2 are used as reference data to evaluate those to compute in each
“higher” class, each class being calculated one after the other, increasing the number of excited modes in the ﬁnal
state. The advantages of using the overlap integrals of these classes are twofold. The ﬁrst one is that these integrals
are computationally cheap and are generated quickly even in the case of large molecules. The second interest lies in
the information provided by the reference data they provide.
Depending on the approximation of the electronic transition dipole moment, FC or FCHT/HT, 2 or 3 sets of
reference data are used for the prescreening. The ﬁrst set F
C
1
is deﬁned during the calculation of the transtions from
class 1 and is used for FC, FCHT and HT calculations. Its elements are deﬁned as:
F
C
1
(i, v
′′
i
) =
1
2v
′′
i
D
i
0
′
 0
′′
+v
′′
i
−1
′′
i
+
2(v
′′
i
−1) C
ii
0
′
 0
′′
+v
′′
i
−2
′′
i
2
(27)
where the he factors C
ii
and D
i
give respectively information on the effect of the shifts in equilibrium positions and
the frequencies on the overlap integrals of overtone, and more precisely on the vibrational progression of mode i.
In case of HT or FCHT calculations, a second set of data is extracted from class 1, H
C
1
, which stores the square
of the pure HerzbergTeller contribution for a given mode i and the corresponding transition 0
′
 0
′′
+v
′′
i
:
H
C
1
(i, v
′′
i
) =
∂µ
if
∂Q
′′
i
0
¯h
2ω
′′
i
v
′′
i
0
′
 0
′′
+v
′′
i
−1
′′
i
+
v
′′
i
+ 1 0
′
 0 +v
′′
i
+ 1
′′
i
2
(28)
Finally, a last set F
C
2
, used for all calculations, is obtained in class 2, and gives information about the Duschinsky
mixing of the normal modes. It contains all combinations of modes i and j but only considering the cases of an equal
number of quanta for both modes (v
′′
i
= v
′′
j
):
F
C
2
(i, j, v
′′
i
= v
′′
j
) =
0
′
 0
′′
+v
′′
i
+v
′′
j
2
−
F
C
1
(i, v
′′
i
) ×F
C
1
(j, v
′′
i
)
0
′
 0
′′
2
(29)
From the previous description, a problem arises to deﬁne the dimensions of the arrays F
C
1
, F
C
2
and H
C
1
, and
more precisely the maximum quantum numbers v
′′
i
max
for classes C
1
and C
2
. Practically, these are set manually. Since
calculations of the FranckCondon integrals in these classes are computationally cheap, a relatively high limit, chosen
to work in most common cases, is considered; C
max
1
= 20 for class 1 and C
max
2
= 13 for class 2. These values can be
set manually in the ReadFCHT section with the keywords MaxC1 (or MaxOvr) for C
max
1
, and the keywords MaxC2
(or MaxCmb) for C
max
2
.
The procedure to generate a vibronic spectrum is as follows. First, calculations are carried out for class C
1
and
then class C
2
. For class C
3
and above, these are done in two steps. The evaluation method is initially called to set
the maximum number of quanta v
′′
i
max
to process for each mode i. To perform this prescreening, an additional limit,
N
max
I
, which represents the maximum number of integrals to compute in a given class is set. This number controls
roughly the computational cost of the overall simulation, but at the risk of a loss in accuracy of the generated spectrum
if it is set too low. A good compromise between resources usage and precision of the spectrum is set by default
(N
max
I
= 10
8
). This parameter can be modiﬁed in GAUSSIAN with the keyword MaxInt given in the ReadFCHT
section (see the keywords list for an explanation of the syntax).
Two thresholds, ǫ
1
and ǫ
2
, are deﬁned for the sets of data F
C
1
and F
C
2
, respectively. In case of FCHT or HT
calculations, a third threshold ǫ
H
1
for H
C
1
is also set. For each mode i, two maximum quantum numbers, respectively
v
C
1
i
max
and v
C
2
i
max
, are obtained by decreasing the number of quanta v
′′
i
until the conditions F
C
1
(i, v
′′
i
) ≥ ǫ
1
for the ﬁrst
set and F
C
2
(i, j, v
′′
i
) ≥ ǫ
2
with j = i for the second set, are met. For FCHT/HT calculations, a similar procedure is
performed with H
C
1
and the condition H
C
1
(k, v
′′
k
) ≥ ǫ
H
1
to obtain the maximum quantum number v
H
i
max
. The highest
of the maximum quantum numbers deﬁned previously is chosen as v
′′
i
max
. Once the set v
′′
max
has been deﬁned, the
corresponding number of integrals to calculate is roughly estimated, for a given class C
n
, as N
I
=
N
C
n
× v
′′
max
n
,
where
N
C
n
represents the number of combinations of the n excited oscillators and v
′′
max
is the arithmetic mean of
the N maximum quantum numbers. If the number of integrals to compute, N
I
is higher than the allowed limit N
max
I
,
8
the thresholds ǫ
1
and ǫ
2
(and ǫ
H
1
for FCHT and HT calculations) are increased and the set of maximum quantum
numbers v
′′
max
is reestimated. When the condition N
I
≤ N
max
I
is fulﬁlled, all transition dipole moment integrals are
computed up to the chosen maximum number of quanta v
′′
i
max
for each mode.
Evaluating the reliability of the prescreening with the sum rules
To check the reliability of the prescreening method, the total intensity calculated after each class is checked with the
total intensity expected using analytic sum rules. The sum of all transition intensities is given by,
I
tot
=
¸
′
ρ
′
¸
′′
Ψ
′
 µ  Ψ
′′
2
≈
¸
v
′
ρ
′
¸
v
′′
v
′
 µ
if
 v
′′
2
(30)
where the ﬁrst sum symbol represents the summation over all possible vibrational initial states and the second one the
ensemble of all ﬁnal states. ρ
′
is the Boltzmann population of each initial state.
Expanding the square in the previous equation and accounting for the orthonormality of the vibrational wave
functions, the intensity I
tot
can be written:
I
tot
=
¸
v
′
ρ
′
v
′
 µ
if
· µ
if
 v
′
(31)
In case of FC calculations, where µ
if
= µ
if
(Q
′′
0
), eq. 31 can be written:
I
tot
=
µ
if
(Q
′′
0
)
2
¸
v
′
ρ
′
v
′
 v
′
=
µ
if
(Q
′′
0
)
2
(32)
In the framework of the HerzbergTeller approximation of the electronic transition dipole moment (FCHT and HT
calculations), the computation of I
tot
is more involved. Considering the Taylor expansion of the electronic transition
dipole moment given in eq. 5, and eq. 31, it is straightforward to see that annihilation and creation operators will be
needed to obtain the sum rules. However, the development of µ
if
in the Taylor series about the equilibrium geometry
of the ﬁnal state is not immediate because the annihilation and creation operators obtained this way act on the quantum
states of the ﬁnal state and not on the initial state, with respect to our previous deﬁnition in eq. 5. A simple solution
would be to develop µ
if
in a Taylor series about the equilibrium geometry of the initial state. However, while the
equality µ
if
= µ
if
(Q
′
) = µ
if
(Q
′′
) is true, this is generally not the case when considering the Taylor series around
each equilibrium geometry. As a consequence, two analytic limits are deﬁned depending on the state of reference,
I
tot
Q
′
for the initial state and I
tot
Q
′′
for the ﬁnal state.
The ﬁrst analytic limit, I
tot
Q
′
is rather straightforward to evaluate:
I
tot
Q
′ =
¸
v
′
ρ
′
v
′

µ
if
(Q
′
0
)
2
+
N
¸
k=1
∂µ
if
∂Q
′
k
0
2
Q
′
k
2
 v
′
(33)
Using the annihilation and creation operators, the analytic limit is given by the formula,
I
tot
Q
′ =
µ
if
(Q
′
0
)
2
+
¸
v
′
ρ
′
N
¸
k=1
∂µ
if
(τ)
∂Q
′
k
0
2
¯h
2ω
′
k
(2v
′
k
+ 1) (34)
In the case of I
tot
Q
′′
, additional steps are needed to evaluate the analytic limit:
I
tot
Q
′ =
¸
v
′
ρ
′
v
′

µ
if
(Q
′′
0
)
2
+
N
¸
k=1
∂µ
if
∂Q
′′
k
0
2
Q
′′
k
2
 v
′
(35)
=
¸
v
′
ρ
′
v
′

µ
if
(Q
′′
0
) +
N
¸
k=1
∂µ
if
∂Q
′′
k
0
N
¸
l=1
J
T
kl
Q
′
l
+
J
T
kl
K
l
2
 v
′
(36)
9
where the inverse of the Duschinsky transformation given in eq. 14 has been used to express Q
′′
with respect to Q
′
.
After using the operators of the second quantization, I
tot
Q
′′
is given by the relation:
I
tot
Q
′′ =
µ
if
(Q
′′
0
)
2
+
¸
τ=x,y,z
¸
v
′
ρ
′
¸
N
¸
k=1
∂µ
if
(τ)
∂Q
′′
k
0
N
¸
l=1
J
T
kl
N
¸
m=1
∂µ
if
(τ)
∂Q
′′
m
0
J
T
ml
¯h
2ω
′
l
(2v
′
l
+ 1)
−2µ
if
(Q
′′
0
, τ)
N
¸
k=1
∂µ
if
(τ)
∂Q
′′
k
0
N
¸
l=1
J
T
kl
K
l
+
N
¸
k=1
∂µ
if
(τ)
∂Q
′′
k
0
N
¸
l=1
J
T
kl
K
l
N
¸
m=1
∂µ
if
(τ)
∂Q
′′
m
0
N
¸
n=1
J
T
mn
K
n
¸
(37)
where the summation over the Cartesian coordinates (x, y, z) is explicitly given.
The choice of I
tot
Q
′
or I
tot
Q
′′
in GAUSSIAN depends on the available data. In the case of absorption, the excited
state is Q
′′
, so µ
if
(Q
′′
0
) and ∂µ
if
/∂Q
′′
are known. Hence, the analytic sum chosen as a reference to evaluate the
convergence of the spectrum is I
tot
Q
′′
. In case of emission, the reference is I
tot
Q
′
.
The chosen analytic limit, I
a
(I
tot
for FC calculations, I
tot
Q
′
or I
tot
Q
′′
for FCHT/HT calculations) is used to calculate
the spectrum convergence (called in the GAUSSIAN output the spectrum progression) with the following relation:
spectrum progression =
¸
v
′ ρ
′
¸
v
′′
v
′
 µ
if
 v
′′
2
I
a
(38)
In the current implementation of GAUSSIAN, the temperature is not yet taken into account, so the relation used in
practice is:
spectrum progression =
0
′
 µ
if
 v
′′
2
I
a
(39)
3 Quick start
In its most concise form, the generation of a vibrationallyresolved electronic spectrum in GAUSSIAN requires a single
keyword representing the terms of the Taylor series given in eq. 5 that must be taken into account.
• FC: zerothorder term of the Taylor series
µ
if
= µ
if
(Q
′′
0
)
, suitable for fullyallowed transitions
• FCHT: zeroth and ﬁrstorder terms of the Taylor series
µ
if
= µ
if
(Q
′′
0
) +
¸
N
k=1
(∂µ
if
/∂Q
′′
k
)Q
′′
k
, suitable
for most cases spanning from fullyallowed to dipoleforbidden transitions
• HT: ﬁrstorder term of the Taylor series
µ
if
=
¸
N
k=1
(∂µ
if
/∂Q
′′
k
)Q
′′
k
, suitable for dipoleforbidden transi
tions or to show the contribution of the HerzbergTeller approximation to the spectrum.
Additionally, GAUSSIAN will need the checkpoint ﬁle containing the data of the ﬁnal state. This ﬁle must be given
after the standard input (in general, below the molecule speciﬁcation), the data for the initial state being taken from
the current calculation.
Two methods can be distinguished to generate the vibrationallyresolved electronic spectra. The ﬁrst one is to
simulate the latter as soon as the frequencies of the initial state have been calculated. In this case, two GAUSSIAN jobs
are required, assuming the structures of the initial and ﬁnal states are already optimized:
1. Calculation of the frequencies for the ﬁnal state
2. Calculation of the frequencies for the initial state followed by the generation of the spectrum.
10
In the input ﬁle for the second step, the keywords FC, FCHT, HT is given in Frequency as follows (the example
below is limited to the case of the FranckCondon approximation):
Link 0 Commands
Route section (# lines) with Frequency=(FC,SaveNM) NoSymm
Title section
Molecule speciﬁcation
Name of the checkpoint ﬁle generated in step 1
In the example above, two additional keywords are used. While not mandatory, SaveNM will make GAUSSIAN
save the frequencies and normal modes in the checkpoint ﬁle. This option is necessary to deal with QM/MM calcula
tions or when dealing with frozen atoms to extract correctly the normal modes and frequencies. As a consequence, it
is advisable to use it every time when computing the frequencies for both states and avoid possible issues caused by
the impossibility of GAUSSIAN to recompute correctly the eigenvalues and eigenvectors of the Hessian matrix.
Since this method requires the computation of frequencies each time a spectrum must be generated, it is not well
suited when diverse parameters must be tried for the generation of the spectrum. A second way of using GAUSSIAN
is through a 3steps procedure where the last step of the previous method is broken down in two separate steps, ﬁrst
the calculation of the frequencies and then the generation of the spectrum. Schematically, this gives the following
procedure:
1. Calculation of the frequencies for the initial state
2. Calculation of the frequencies for the ﬁnal state
3. Generation of the electronic spectra
The order in which the ﬁrst two steps are performed is not important and they can be done simultaneously. We
will however consider this sequence is respected in the following description
While this method seems more complex, it is also more ﬂexible as GAUSSIAN works as a standalone program
dedicated to the simulation of the electronic spectra. The input ﬁles for the ﬁrst two steps are classical ones to compute
frequencies with the keyword SaveNM used in Frequency. The input ﬁle for the last step is as follows:
Link 0 Commands
%Chk=Name of the checkpoint ﬁle generated in step 1
#P Geometry=AllCheck Frequency=(ReadFC,FC,SaveNM) NoSymm
Name of the checkpoint ﬁle generated in step 2
The options Geometry=AllCheck and Frequency=ReadFC are described in the GAUSSIAN manual. Ba
sically, they let us extract all necessary data from the checkpoint ﬁle given in the line starting by %Chk= without the
need to perform long calculations before the procedure to generate the spectrum is called.
As mentioned before, this approach is particularly interesting when investigating the best settings to generate an
accurate electronic spectrum, using the parameters described in the section below.
11
Description of the output
Whatever the chosen procedure, the output will be similar and structured as follows. The block in the output related
to the generation of the spectrum starts with the following output:
**********************************************************************
Generation of the FranckCondon spectrum
**********************************************************************
General information is then given on the type of calculation, the approximation of the electronic transition dipole
moment and the type of transition:
Approx. of the electronic transition dipole moment: FC
Type of transition requested: ONEPHOTON ABSORPTION
The output presented above is an example showing the case of an absorption spectrum with the electronic transition
dipole moment considered as constant during the transition.
GAUSSIAN then describes the procedure of extraction of the data from the sources. In the case of our quick start
procedure. the output will be:
Data for initial state taken from current calculation.
Passedin normal modes used.
Data for final state taken from checkpoint file "checkpoint ﬁle of step 1"
Normal modes recovered from file.
Initial state structure is set in Eckart orientation.
Final state structure is superposed to it.
The last line is followed by the geometry of the system in both states after reorientation. As explained in the de
scription of the FranckCondon principle, the calculation of the vibronic spectra requires the minimization of nuclear
displacements during the transition. Although rigorous separation between rotations and vibrations is, of course, not
possible, their coupling for the initial electronic state can be minimized by putting the molecule in the Eckart orienta
tion (origin in the mass center and Cartesian axes along the principal inertia moments) using the standard GAUSSIAN
orientation for the ordering of Cartesian axes. Two options are next possible for the ﬁnal electronic state, namely to
use its own Eckart orientation, or to minimize the angular momentum between initial and ﬁnal structures. The second
one is the default because it minimizes the contribution of rotations to the shift vector and the Duschinski matrix.
Next, the molecule in the ﬁnal electronic state is ﬁrstly rotated using the same rotation matrix of the reference
state and next a new rotation matrix is computed in order to minimize the angular momentum between initial and ﬁnal
structure
N
A
¸
i=1
M
ii
X
′
i
∧ X
′′
i
(40)
where M is the diagonal matrix of the atomic masses, X
′
i
and X
′′
i
are the triplets of Cartesian coordinates for the
nucleus i in the initial and ﬁnal states, respectively.
This two step procedure [10] allows to avoid numerical problems when the geometries and/or starting orientations
of initial and ﬁnal states are strongly different. There are two options to build the rotation matrix, using Euler angles
[11–13] or quaternions [14,15], respectively. Although the latter approach (which is the default) should be more stable
and direct, there are cases in which it fails, so that, after a predetermined number of iterations, the program shifts to
Euler angles.
The actual calculation is then presented:
12

Overlap integrals computation

Energy of the 00 transition: Calculated value cmˆ(1)
Notes about the overlap integrals description:
 DeltaE is the relative energy of the transition (wrt 00)
 TDMIˆ2 is the square of the transition dipole moment integral
 Intensity is the line intensity (absolute value)
A list of the most intense transitions is then printed. They are listed by incrementing class. The general format is:
Initial State: <0
Final State: xˆx,xˆx>
DeltaE = x.xxxx  TDMIˆ2 = x.xxxxExxx, Intensity = x.xxxxExxx
........................................
The ﬁrst line represents the initial state and the second line the ﬁnal state. The third line contains the energy of the
transition with respect to the energy of the transition between the vibrational ground state, 0
′
 0
′′
, the value
 v
′
 µ
if
 v
′′

2
, and the intensity of the corresponding spectrum line. The character x given above represents a
digit or a sign.
Once a class has been treated, the convergence of the spectrum is printed:
++ Spectrum progression: xx.xx%
Finally, the spectrum generated by GAUSSIAN is printed:
++
 Final Spectrum 
++
Axis X = Energy (in cmˆ1)
Axis Y = Intensity (in arbitrary units)

xxxxx.xxxx x.xxxxxxDxxx
4 List of options
While the default behavior of GAUSSIAN is set to give satisfactory results in most cases, it can be not well suited for
particular cases or poorly adapted to speciﬁc requirements from the user. A number of options exist to extensively
parameterize the calculations and provide a satisfactory analysis of the case of interest. These options need to be given
in a speciﬁc section referred to as the “ReadFCHT section”. This section lies below the standard GAUSSIAN input
and is activated by adding the keyword “ReadFCHT” in the option Frequency. The resulting GAUSSIAN input is
structured as follows:
13
Link 0 Commands
Route section (# lines) with Frequency=(ReadFCHT)
Title section
Molecule speciﬁcation
Optional additional sections used by links called before l716
ReadFCHT section
The description of the different sections above the ReadFCHT section can be found in the GAUSSIAN 09 manual
and is outside the scope of this document. The options available for the simulation of vibronic spectra using the
FranckCondon principle are listed in the table below, organized by functions. To make the reading of the latter easier,
the lines are differentiated by alternating backgrounds of different colors. Following this scheme, two keywords in the
same “line” are equivalent (ex: ABS and ABSORPTION). Additionally, blocks are deﬁned between two consecutive
horizontal black lines. All keywords given in the same block of lines correspond to the same option and are mutually
exclusive (ex: FC, FCHT and HT). In general, when several keywords related to the same option are given, only the
last one is taken into account and the others are discarded.
Note: Regarding the last group of options dealing with forced calculations, it is highly advisable to avoid their
use by default as they will bypass protections of GAUSSIAN regarding the soundness of the calculations. As a conse
quence, they should be used carefully.
Keyword Values Description
General parameters of the calculations
FC None (Default) The electronic dipole moment is assumed constant during the
transition. This approximation is generally well suited for fullyallowed
transition.
FCHT None The electronic transition dipole moment is developped in a Taylor series
about the equilibrium geometry of the ﬁnal state up to the ﬁrstorder
term included. This approximation is more general than FC and works
on diverse cases, from fullyallowed to dipoleforbidden transitions.
HT None Only the linear variation of the electronic transition dipole moment with
the normal coordinates of the ﬁnal state is taken into account (ﬁrstorder
term of the Taylor series given in eq. 5).
ABSORPTION
ABS
None (Default) The simulated vibronic spectrum corresponds to a onephoton
absorption transition.
EMISSION
EMI
None The simulated vibronic spectrum corresponds to a onephoton emission
transition.
Sources of input data
CALC1 None (Default) Data for the initial state are taken from the current GAUSSIAN
job.
CHK1 None Data for the initial state are taken from the checkpoint ﬁle provided
below the ReadFCHT section.
OUT1 None Data for the initial state are taken from the GAUSSIAN output ﬁle pro
vided below the ReadFCHT section.
CALC2 None Data for the ﬁnal state are taken from the current GAUSSIAN job.
14
Keyword Values Description
CHK2 None (Default) Data for the ﬁnal state are taken from the checkpoint ﬁle pro
vided below the ReadFCHT section.
OUT2 None Data for the ﬁnal state are taken from the GAUSSIAN output ﬁle pro
vided below the ReadFCHT section.
NSTATE 1 Chooses the electronic state from which the data relative to the elec
tronic transition dipole moments and the derivatives are taken.
Usergiven input data or modiﬁcation options
InpDEner 0.0 (= Off) Replaces the calculated difference of energy between both electronic
states involved in the transition by the value given by the user. Such
value is expected in Hartree and is not taken in account if null.
SclVec None A modespeciﬁc scaling algorithm based on the Duschinsky matrix is
used to compute new frequencies for the ﬁnal state using the differences
between the calculated frequencies for the initial states and usergiven
ones listed below the ReadFCHT section. The frequencies are expected
in cm
−1
. See ref. [16] for more details on its behavior.
JDusch None (Default) Uses the correct Duschinsky matrix to perform the calcula
tions.
JIdent None Uses an identity matrix instead of the Duschinsky matrix. In this case
the modemixing is ignored.
Parameterization of the GAUSSIAN output
PRTMAT 0 (= Off) Prints the Sharp and Rosenstock matrices or the Duschinsky matrices
and vectors. A digit is assigned to each matrix as follows:
1. Duschinsky matrix J. Please note that, with respect to eq. 14, J
T
is printed.
2. shift vector K
3. Sharp and Rosenstock matrix A
4. Sharp and Rosenstock vector B
5. Sharp and Rosenstock matrix C
6. Sharp and Rosenstock vector D
7. Sharp and Rosenstock matrix E
The digits corresponding to the matrices to be printed are placed side
by side to form a number that is given as the value of PRTMAT. Ex:
PRTMAT=12 corresponds to printing the Duschinsky matrix and shift
vector.
ALLSPECTRA None Prints the spectra corresponding to each class in addition to the ﬁnal,
total spectrum.
PRTINT 0.01 Prints data (assignment, energy, intensity) of the transitions which have
an intensity ( v
′
 µ
if
 v
′′

2
) above or equal to 1% of the total
analytic limit.
Setting of the spectrum layout
15
Keyword Values Description
SPECMIN 1000.0 Sets (in cm
−1
) the lower bound of the spectrum. The value is normally
given relative to the energy of the transition between both vibrational
ground states.
SPECMAX +8000.0 Sets (in cm
−1
) the upper bound of the spectrum. The value is normally
given relative to the energy of the transition between both vibrational
ground states.
NORELI00 None Using this keyword, GAUSSIAN expects the lower and upper bound of
the spectrum to be given in absolute values (not relative to the 00 tran
sition). This keyword should be used together with both SPECMIN and
SPECMAX to avoid an unexpected behavior.
SPECRES 8.0 Resolution of the spectrum given by the difference of energy between
two contiguous measuring points (in cm
−1
). It is noteworthy that a
very high resolution (given by a small value of SPECRES) can greatly
hamper the computational speed of the spectrum generation.
SPECHWHM 135.0 Sets the HalfWidth at HalfMaximum (in cm
−1
) for the convolution of
the spectrum using a Gaussian distribution. A large value of SPECHWHM
coupled to a small value of SPECRES can cause a steep increase of the
computational times.
Modiﬁcation of the behavior of the a priori scheme to chose the most relevant transition
MAXOVR
MAXC1
20 Sets the maximum quantum number that has to be considered for each
mode of C
1
(C
max
1
).
MAXCMB
MAXC2
13 Sets the maximum quantum number to consider for each mode involved
in the combination bands in C
2
(C
max
2
).
MAXINT 100 Sets the maximum number of integrals (N
max
I
, expressed in million) to
compute for each class above C
2
.
NOINTAN None Deactivates the usage of analytic formulae to compute the overlap inte
grals in classes C
1
and C
2
. By default, analytic formulae are used when
available for these classes.
Termination criteria for the spectrum generation
MAXBANDS 7 Sets the maximum class to consider. Calculations can end before if
there are not enough excited modes or DELTASP is also deﬁned and the
condition imposed by the latter is met before.
DELTASP 0.0 Sets a condition on the spectrum convergence. If the spectrum progres
sion with respect to the total intensity between two consecutive classes
is below DELTASP (in absolute value), then the calculations end.
Forcing calculations
4
ForceFCCalc None Forces the calculation of the FranckCondon integrals even if the overlap
integral between the vibrational ground states of the initial and ﬁnal
states is very low ( 0
′
 0
′′

2
< 10
−4
).
ForcePrtSpectrum None Forces the printing of the ﬁnal spectrum even if the total progression is
low (below 50%).
The structure of the GAUSSIAN input ﬁle starting from the ReadFCHT section is as follows, each optional block
of data (“SclVec” and “Sources”) being terminated by a blank line:
4
Warning: The keywords describe in this section should be used with care as they might lead to results whose reliability is unpredictable
16
ReadFCHT section
[blank line]
Usergiven frequencies for the initial state (necessary for SclVec)
[blank line]
Name of the ﬁle containing the data for the initial state (if different from the cur
rent GAUSSIAN job)
Name of the ﬁle containing the data for the ﬁnal state (if different from the cur
rent GAUSSIAN job)
[blank line]
‘‘SclVec’’ block
‘‘Sources’’ block
By default, only the name of the checkpoint ﬁle containing the data of the ﬁnal state needs to be given after the
ReadFCHT section.
5 Some practical examples
The examples described here are taken from reference [17] and shows the parameters used in the ReadFCHT section
to carry out the calculations. The GAUSSIAN inputs presented here are based on the 3steps usage of GAUSSIAN,
where the last step is dedicated to the generation of the spectrum.
Photodetachment spectrum of SF
−
6
: parameterizing the prescreening method
In the photodetachment spectrum of SF
−
6
, a signiﬁcant elongation of the SF bond upon electron attachment is found.
As a consequence, the potential curves of the normal mode corresponding to the SF symmetric stretching are no
ticeably displaced (see Fig. 2 in ref [18]). When generating the photodetachment spectrum of SF
−
6
with the standard
parameter, an insufﬁcient value of MAXC1 is set and only a partial spectrum is obtained. As a consequence, the
following input ﬁle is used for the generation of the complete spectrum:
%Chk=SF6_neutral_freq.chk
#P Geom=AllCheck Freq=(ReadFC,FC,SaveNM,ReadFCHT) NoSymm
PRTMAT=12 MAXC1=100 MAXBANDS=4 SPECHWHM=0.5
SF6_anion_freq.chk
C
max
1
is set to a safe, high value since the cost of the prescreening is cheap. When performing the calculation,
GAUSSIAN will ﬁnd that it does not need to go up to class 7 and will safely stop the calculations. Here, we set
manually the correct limit.
S
1
←S
0
absorption spectrum of Anisole: parameterizing the spectrum layout
To compare the theoretical spectrum obtained with GAUSSIAN and the experimental REMPI spectrum, it is necessary
to modify the default values of the parameters corresponding to the spectrum layout. This is done with the following
input
%Chk=anisole_S0.chk
#P Geom=AllCheck Freq=(ReadFC,FC,SaveNM,ReadFCHT) NoSymm
PRTMAT=12 NORELI00 SPECMIN=37900 SPECMAX=42000 SPECHWHM=1. SPECRES=1.
anisole_S1.chk
17
The absolute values of the spectrum bounds are given here and a very ﬁne spectrum is requested.
Although the spectrum layout obtained this way is very similar to the experimental one, an energy shift was
observed for several peaks, with the frequencies calculated at the harmonic level. To correct this, anharmonic fre
quencies had to be used. However, they could not be straightforwardly obtained for the ﬁnal, excited state with the
timedependent density functional theory (TDDFT) computations. Hence, the modespeciﬁc scaling scheme [16] im
plemented in GAUSSIAN and available with the keyword SclVec was used. The anharmonic frequencies calculated
for the ground state [19] were used as input as follows:
%Chk=anisole_S0.chk
#P Geom=AllCheck Freq=(ReadFC,FC,SaveNM,ReadFCHT) NoSymm
PRTMAT=12 NORELI00 SPECMIN=37900 SPECMAX=42000 SPECHWHM=1. SPECRES=1.
SclVec
86.39 200.38 252.59 257.52 417.46 437.57 510.86 554.26 623.74
696.93 757.21 784.32 811.61 883.10 958.95 981.60 994.62 1018.63
1040.32 1082.75 1146.70 1164.42 1177.75 1177.40 1238.75 1305.54 1336.45
1467.80 1454.61 1479.55 1465.73 1494.69 1582.76 1601.40 2869.62 2902.51
2993.57 3006.94 3042.47 3047.04 3068.53 3077.61
anisole_S1.chk
GAUSSIAN then corrects the harmonic frequencies of the excited state with a modespeciﬁc scaling to account for
the anharmonicity. Using the harmonic frequencies present in the checkpoint (ω
′
harm
) and the usergiven data (ω
′
anh
),
a scaling vector α
′
is calculated:
α
′
i
= ω
′
anh
/ω
′
harm
Using the square elements of the Duschinsky matrix, the scaling vector for the excited state α
′′
is deduced from
α
′
with the relation,
α
′′
j
=
N
¸
i=1
J
ij
2
α
′
i
The new anharmonic frequencies ω
′′
anh
are then calculated as:
ω
′′
anh
= α
′′
i
ω
′′
harm
GAUSSIAN prints in output the scaling vectors α
′
and α
′′
as well as the frequencies that will be used in each state
for the calculation of the vibonic spectrum.
6 Description of the errors reported by GAUSSIAN
Several controls are performed in GAUSSIAN to check the validity of the calculations. Depending on the origin of
the problem found, calculations can be aborted with an error or a simple warning can be issued. While the former
will result in a termination of the calculations, the latter are there to draw the attention of the user on potential issues.
In this section, we present a brief overview of the most common error and warning messages, their origin as well as
possible workarounds or leads that should be investigated to solve them.
Errors
 Cannot extract data for both states from the current calculations
This error is due to the fact that GAUSSIAN attempts to extract all data from the current job.
18
It is likely that CALC1 has been given without setting the source of data for the ﬁnal state. By default, GAUSSIAN
will have set the current calculation for the ﬁnal state.
 WARNING: Charge (or Multiplicity) is different between initial and ﬁnal states. Calc. cannot be done out
with the trans. dip. mom. in the data ﬁles
This error is raised if a FCHT or HT calculation is requested and GAUSSIAN cannot use the transition electronic
dipole moment and its derivatives that were found in the source ﬁles.
For this kind of calculation, the transition is generally fullyallowed and the FCapproximation should be sufﬁcient.
 ERROR: The FranckCondon factor corresponding to the overlap integral between both vibrational ground
states is too small: <0’0">ˆ2 = x
This error indicates that it is very likely that the underlying theory used to generate the spectrum, the Franck
Condon principle, is unsuitable for the case of interest. This is a typical issue when the equilibrium geometry of the
initial and ﬁnal states are noticeably different. This can happen when one of the structures is planar in one electronic
state and not planar in the other electronic state.
Another indicator of this problem is the Duschinsky matrix (which can be displayed with the option “PRTMAT=1”
in the ReadFCHT section) that shows the projection of the normal modes of one state on those of the other state. In
this case, the Duschinsky matrix is rather diffuse, that is to say that many normal coordinates of the ﬁnal state are
expressed by a combination of a rather large number of normal modes of the initial state.
If the calculations must be carried anyway, this error can be bypassed with the keyword ForcedFCCalc. How
ever, please note that the resulting spectrum will be likely unreliable and the corresponding calculations should be
considered as tests.
 ERROR: The ﬁnal spectrum progression is too low and the resulting spectrum may be unreliable. To print
the spectrum nevertheless, please use the keyword FORCEPRTSPECTRUM.
This error is often related to the same reasons as the previous one, that is to say that the FranckCondon principle
can be unsuitable to the case of interest.
If this it is not the case, the problem may be caused by too low number of calculated transitions. Several options
may resolve this problem. The ﬁrst one is to increase MAXBANDS which correspond to the highest class to be treated.
If it has been set very low, then the spectrum convergence will be limited. Other possibility is that the values of
MAXC1/MAXOVR and/or MAXC2/MAXCBI are set too low. If this is the case, warnings should have been issued during
the calculations:
Warning: insufﬁcient num. of quanta for mode i,
Finally, this error can also be caused by a low number of transitions to compute in each class (MAXINT).
Warnings
 WARNING: Value for PRTINT is too low. Reset to 1.0D6. Be careful that it can cause a very verbose output
of Gaussian.
Setting a very low value of PRTINT might cause the generation of a very large output ﬁle. PRTINT is given as a
fraction of the total analytic sum. As a consequence, setting PRTINT=1.D3 for example will print the assignment
of all integrals which contribute to at least 0.1% to the total intensity.
 Warning: insufﬁcient num. of quanta for mode i,
GAUSSIAN found that the condition F
C
1
(i, C
1
max
) ≥ ǫ
1
was true for the normal mode i. Such a condition means
that the parameter MAXC1 must be set with a higher value that the current one (by default, MAXC1=20).
References
[1] J. Franck, Transactions of the Faraday Society 21, 536 (1926).
[2] E. Condon, Physical Review 32, 858 (1928).
[3] F. Santoro, R. Improta, A. Lami, J. Bloino, and V. Barone, The Journal of Chemical Physics 126, 084509 (2007).
[4] F. Santoro, R. Improta, A. Lami, J. Bloino, and V. Barone, The Journal of Chemical Physics 128, 224311 (2008).
19
[5] C. Eckart, Physical Review 47, 552 (1935).
[6] G. Herzberg and E. Teller, Zeitschrift f¨ ur Physikalische Chemie  Abteilung B 21, 410 (1933).
[7] F. Duschinsky, Acta Physicochimica URSS 7, 551 (1937).
[8] T. E. Sharp and H. M. Rosenstock, The Journal of Chemical Physics 41, 3453 (1964).
[9] P. T. Ruhoff, Chemical Physics 186, 355 (1994).
[10] B. Van der Veken, G. Pieters, and M. Herman, Theochem 91, 387 (1983).
[11] S. Ehrenson, Journal of the American Chemical Society 96, 3778 (1974).
[12] W. Miller, B. Ruf, and Y. Chang, The Journal of Chemical Physics 89, 6298 (1988).
[13] C. Zhixing, Theoretical Chemistry Accounts 75, 481 (1989).
[14] G. Kneller, Molecular Simulation 7, 113 (1991).
[15] G. Kneller, The Journal of Chemical Physics 88, 2709 (1991).
[16] J. Bloino, M. Biczysko, O. Crescenzi, and V. Barone, The Journal of Chemical Physics 128, 244105 (2008).
[17] V. Barone, J. Bloino, M. Biczysko, and F. Santoro, Journal of Chemical Theory and Computation 5, 540 (2009).
[18] J. C. Bopp, J. R. Roscioli, M. A. Johnson, T. M. Miller, A. A. Viggiano, S. M. Villano, S. W. Wren, and W. C.
Lineberger, Journal of Physical Chemistry A 111, 1214 (2007).
[19] V. Barone, The Journal of Chemical Physics 122, 014108 (2005).
20
Contents
1 2 3 4 5 6 Introduction Theoretical background Quick start List of options Some practical examples Description of the errors reported by G AUSSIAN 2 2 10 13 17 18
1 Introduction
In this new release of G AUSSIAN, it is possible to compute vibrationallyresolved absorption and emission spectra. This white paper aims at introducing the general theory underlying such calculations and presenting the possibilities offered to generate electronic spectra inside G AUSSIAN. The document is divided as follows. After a brief introduction of the basic theory used in G AUSSIAN to generate vibronic spectra, a quick presentation of its basic usage is given. The main features of the input and output will then be described. The second part of the document is devoted to more advanced cases and to the tools to control and ﬁnetune the calculations to meet speciﬁc needs. The available options and their purpose will be listed, followed by examples of applications showing the usage of the most common ones. The last part summarizes the most common errors reported by G AUSSIAN and possible workarounds. This section is not aimed at being exhaustive and alternative solutions can work as well or even be more adapted to some particular cases. The following typographic conventions will be used thereafter: • ′ : placed next to a letter/symbol, refers to the initial state • ′′ : placed next to a letter/symbol, refers to the ﬁnal state • NA : represents the number of atoms in the molecule or system of interest • N : represents the number of normal modes in the molecule or system of interest • M: designates a matrix or vector • Mi or M(i): represents the ith element of vector M • Mij or M(i, j): represents the i, j element of matrix M Note: For convenience, the notation adopted in this document is slightly different from the spectroscopic conventions since the relative energies of the initial and ﬁnal states are not taken into account when using ′ and ′′ . This allows to treat indifferently the similar cases of absorption and emission without duplicating the formulae.
2 Theoretical background
The theoretical description in this section is not intended to be exhaustive but rather to give a sufﬁcient background in order to use G AUSSIAN for the simulation of vibrationally resolved electronic spectra. It is divided in three subsections. The ﬁrst one presents a general theoretical background and the approximations used to compute the transition dipole moment and the transition intensities. This will help to understand the possibilities given by the FranckCondon principle as well as the limit of such a method. The second part deals with the prescreening method used by G AUS SIAN to choose a priori the most intense transitions. The parameters on which it relies as well as their inﬂuence are described there. Finally, a discussion on the guessing of spectrum convergence is carried out.
2
during a transition. In the treatment presented here. since the analytic form of the electronic transition dipole moment is unknown. respectively.Calculation of the transition dipole moment Line intensities in onephoton absorption and emission spectra depend on the square of the transition dipole moment Ψ′  µ  Ψ′′ as well as on the radiation frequency (ω)2 : σ(ω)abs = σ(ω)emi = 4π 2 ω 3c 4ω 3 3¯ c3 h ρ′ ′ ′′ Ψ′  µ  Ψ′′ Ψ′  µ  Ψ′′ ′′ 2 δ(E ′′ − E ′ − ¯ ω) h (1) (2) ρ′ ′ 2 δ(E ′′ − E ′ + hω) ¯ where ρ′ is the Boltzmann population of each initial state and σ(ω) is the rate of photon absorption (or emission) per molecule and per unit of radiant energy. to develop the electronic transition dipole moment in a Taylor series about the equilibrium geometry of one state of reference. a more ﬂexible approach is adopted here. schematically shown in ﬁgure 2. so that the nuclear wave function can be. describing the ith vibration of the molecule. Since this approximation is very restrictive by assuming that the electronic transition dipole moment remains constant during the transition. with a good accuracy. since the shifts of the nuclear positions in the molecule are often fairly small during the electronic transition. which is the ﬁnal state in our case: N µif (Q ) ≃ ′′ µif (Q′′ ) 0 + k=1 ∂µif ∂Q′′ k Q′′ k 0 1 + 2 N N k=1 l=1 ∂ 2 µif ∂Q′′ ∂Q′′ k l Q′′ Q′′ + . In the method implemented in G AUSSIAN. An additional approximation is done by using the FranckCondon principle. the transition dipole moment can ﬁnally be written. where Qi is one of the N normal coordinates. ′ ′′ Ψ′  µ  Ψ′′ ≈ ψv  µif  ψv (4) ′ ′′ where µif = ψe  µ  ψe is the electronic transition dipole moment. these approximations are not yet sufﬁcient to compute the transition dipole moment. . The underlying theory is that. In the frame of the BornOppenheimer approximation. the most intense transition will be from the chosen initial state to a ﬁnal state being at a minimum of the lowest potential surface vertically upward. As a consequence. the translational part being completely separated from the other two and discarded here. Ψ′ and Ψ′′ represent the molecular wave functions of the initial and ﬁnal state. the second term of the rhs in the previous equation vanishes. it is possible to write the molecular wave function Ψ as a product of an electronic wave function ψe and a nuclear wave function ψn . Using both approximations. the harmonic approximation is also used. it is possible to write the multidimensional vibrational wave function ψv as a product of monodimensional wave functions ψvi (Qi ). G AUSSIAN does not take into account the constant part to calculate the intensity of the spectrum lines 3 . . However. Following this principle. separated into a rotation and a vibrational contribution. We further assume that the Eckart conditions [5] are met. Indeed. rotational energies are considered sufﬁciently small and will not be taken into account. The transition dipole moment can then be written. the electron jump in a molecule takes place in such a short time that the relative positions and velocities of the nuclei are nearly unaltered by the molecular vibrations. ′ ′ ′′ ′′ ′ ′ ′′ ′′ Ψ′  µ  Ψ′′ = ψe ψn  µe  ψe ψn + ψe ψn  µn  ψe ψn (3) Since the electronic wave functions are orthogonal to each other. k l 0 (5) where Q′′ represents the equilibrium geometry of the ﬁnal state. proposed by Franck [1] and mathematically formalized by Condon [2]. 0 2 With respect to the formulae presented here. with a good approximation. it is possible.
However. 6 can be rewritten. in this form.The zeroth order term corresponds to a static electronic transition dipole. Hereafter. (6) + 1 2 k=1 l=1 ∂ 2 µif ∂Q′′ ∂Q′′ k l ′′ ′ ψv  Q′′ Q′′  ψv k l 0 ′ ′′ The overlap integral ψv  ψv is also referred to as the FranckCondon integral. 5. 5. In addition. Following this principle. It is necessary to consider a variation of the dipole moment during the transition. As a consequence. Figure 2: The FranckCondon prinand FCHT both terms. it is referred as the FranckCondon (FC) approximation. ciple is shown by the vertical dotted Using eq. it is necessary to transform them in more versatile and usable FranckCondon integrals. the second term integral in the rhs of eq. A ﬁrst approximation is to account for a linear variation of the dipole moment with the normal coordinates. When dealing with fullyallowed transitions (µif (Q′′ ) ≫ 0). Herzberg and Teller considered the initial state as the state of reference for the linear variation of the electronic transition dipole moment. This is done by using the creation and annihilation operators from the second quantization. generalized to any problem. This is a direct application of the FranckCondon principle mentioned above. missing the most intense vibronic transitions. as approximation of µif . this approximation generally 0 gives very good results. 9. the transition dipole moment can be written: Ψ µΨ ′ ′′ = µif (Q′′ ) 0 N ′ ψv  ′′ ψv ′ ′′ ψv  Q′′  ψv k 0 + k=1 N ∂µif ∂Q′′ k N line. the Taylor expansion of the electronic transition dipole moment is supported up to the second term in the rhs in eq. To simplify the calculation of the integrals given in equation 6. 5. the approximation of µif will be limited to the FranckCondon and HerzbergTeller terms. We use here a more general interpretation of their work by applying to any state of reference. this approximation is not describing correctly the overall spectrum. As a consequence. The integrals in the second and third terms of equation 5 depend on the normal coordinates and therefore cannot be. the vibrational wave function wil be replaced from now on by a vector “v ” containing the quantum numbers vi representing the same vibrational state described by ψv : N v =  ψv = i=1 ψvi Using eq. HT the second one. in the case of weaklyallowed (µif (Q′′ ) ∼ 0) or dipoleforbidden 0 ′′ (µif (Q0 ) = 0) electronic transitions. the highest probability of transition corresponds to 0′  2′′ where the overlap of the wave functions is the highest. the FC approximation considers only the ﬁrst term in the rhs of eq. deﬁned as i a† = i ai = Hence. This corresponds to the ﬁrst order of the Taylor expansion and is referred as the HerzbergTeller [6] (HT) approximation3 . Qi = ωi 2¯ h ωi 2¯ h h ¯ 2ωi d dQi d Qi + dQi Qi − 1/2 (7) (8) ai + a† i (9) In the current implementation. respectively a† and ai . 4 . v ′  Q′′  v ′′ = k 3 h ¯ ′′ 2ωk ′′ vk v ′  v ′′ − 1′′ + k ′′ vk + 1 v ′  v ′′ + 1′′ k (10) In their original work.
To overcome this. M is the diagonal matrix of atomic masses and ∆X is a vector representing the shift of nuclear Cartesian coordinates between the initial and ﬁnal states. while the overlap integral between the vibrational ground states 0′  0′′ can be straightforwardly calculated. and K is the shift vector due to the changes in geometry between the initial and ﬁnal states. it is possible to write the transition dipole moment integral as a combination of overlap integrals: Ψ′  µ  Ψ′′ =µif (Q′′ ) v ′  v ′′ 0 N + k=1 ∂µif ∂Q′′ k 0 h ¯ ′′ 2ωk ′′ vk v ′  v ′′ − 1′′ k (11) + The overlap integrals are given by the equation. 6. this is generally not the case for v ′  v ′′ where v ′ and/or v ′′ are not null. A more versatile method based on recursive formulae [9]. respectively. from the energy perspective. dQ′′ 1 N i=1 Hvi′ (Γ′ i Q′ )Hvi′′ (Γ′′ i i (12) 1 T T × exp − (Q′ Γ′ Q′ + Q′′ Γ′′ Q′′ ) 2 where Γ′ and Γ′′ are the diagonal matrices of the reduced frequencies from the initial and ﬁnal states.where  v ′′ + 1′′ represents. v v ′ ′′ ′′ vk + 1 v ′  v ′′ + 1′′ k =π −N/2 det Γ Γ ′ ′′ 1/4 N −1/2 det(J) N 1/2 i=1 2 2 1/2 ′ ′′ vi vi (vi′ !)(vi′′ !) 1/2 ′′ Qi ) +∞ × −∞ dQ′′ . 10 in eq. 5 . 12 arises from the fact that each vibrational wave function is expressed in a different set of normal coordinates. J and K can be printed in G AUSSIAN with the keyword PrtMat in the ReadFCHT section (with the respective values 1 and 2 as shown in the keywords list). However. Among the several computational approaches proposed till now. . This transformation is generally a good approximation. . their original work was based on analytic formulae for each possible combination of v ′ and v ′′ and it is not adapted when dealing with a large number of normal modes. o ¯ ′′ ¯ ′′ Inserting eq. Q′ = JQ′′ + K (14) where J is called the Duschinsky matrix and represents the mixing of the normal modes during the transition. which follows a similar formalism is described here. The rotation or Duschinsky matrix and shift vector are given by: J = L′ K= L −1 L′′ M1/2 ∆X (15) (16) ′ −1 where L′ and L′′ are the transformation matrices from massweighted Cartesian coordinates to normal coordinates. the linear transformation proposed by Duschinsky [7] to express the normal coordinates of one state with respect to the other’s is used. a vibrational state which differs from the state represented i by  v ′′ by the eigenvalue of the monodimensional Schr¨ dinger equation Evi′′ +1 = hωi (vi′′ + 1/2) = Evi′′ + hωi . and Hvi (qi ) is a Hermite polynomial of degree vi deﬁned by: Hvi (qi ) = (−1)vi eqi 2 dvi −qi 2 vi e dqi (13) A ﬁrst issue to calculate the integral in eq. we have selected the Sharp and Rosenstock’s one [8]. In addition. when the molecule does not undergo a noticeable distortion during the transition.
First. Hv ′ (Γ′ and Hv ′′ (Γ where ′′ 1/2 1/2 Q′ ) = ∂v 1/2 exp −T2 + 2TT Γ′ Q′ ∂Tv ′ ′′ ′ (17) T=0 Q )= ′′ ∂v 1/2 exp −U2 + 2UT Γ′′ Q′′ v ′′ ∂U ′′ ′ ′ ′ (18) U=0 ′ ∂ v1 ∂ v2 ∂ vN ∂v ′′ = ′′ ′′ . 17 and 18. the following formula is obtained: v ′  v ′′ = π −N/2 det Γ′ Γ′′ ′ ′′ 1/4 det(J)1/2 2v 2v v ′ !v ′′ ! dQ′′ exp ′ ′′ −1/2 × ∂v ∂v exp −T2 − U2 ∂Tv ′ ∂Uv ′′ T 1 ′′ T T ′ Q J Γ JQ′′ 2 T (20) + Q′′ JT Γ′ K + KT Γ′ JQ′′ + KT Γ′ K + Q′′ Γ′′ Q′′ + 2UT Γ′′ 1/2 Q′′ + 2TT Γ′ 1/2 JQ′′ + 2TT Γ′ 1/2 K T=U=0 After developing and integrating the previous equation. 6 and 7 as shown in the keywords list). ′ v v vN ∂Tv ∂T11 ∂T22 ∂TN (19) Replacing the Hermite polynomials in eq.. and using the Duschinsky transformation. 6 . 12 by their deﬁnitions given in eqs. .. 4. are deﬁned to be nearnull so that. 5. T and U. we obtain: v v ′ ′′ ∂v ∂v det(J) 1/4 = 2 2 v !v ! 2N/2 det Γ′ Γ′′ v ′ ∂Uv ′′ ∂T det JT Γ′ J + Γ′′ 1 1 × exp − KT Γ′ K + KT Γ′ J(JT Γ′ J + Γ′′ )−1 JT Γ′ K 2 2 v ′ v ′′ ′ ′′ −1/2 ′ ′′ 1/2 × exp UT (2Γ′′ 1/2 (JT Γ′ J + Γ′′ )−1 Γ′′ 1/2 − I)U (21) − I)T 1/2 × exp −2KT Γ′ J(JT Γ′ J + Γ′′ )−1 Γ′′ × exp TT (2Γ′ 1/2 1/2 U 1/2 J(JT Γ′ J + Γ′′ )−1 JT Γ′ × exp −2KT (Γ′ J(JT Γ′ J + Γ′′ )−1 JT − I)Γ′ × exp UT 4Γ′′ 1/2 T (JT Γ′ J + Γ′′ )−1 JT Γ′ 1/2 T To simplify the notation. 5 matrices referred to hereafter as Sharp and Rosenstock matrices are deﬁned: A = 2Γ′ 1/2 J(JT Γ′ J + Γ′′ )−1 JT Γ′ (JT Γ′ J + Γ′′ )−1 Γ′′ 1/2 1/2 −I B = −2Γ′ C = 2Γ′′ E = 4Γ′′ 1/2 (J(JT Γ′ J + Γ′′ )−1 JT Γ′ − I)K −I (JT Γ′ J + Γ′′ )−1 JT Γ′ K 1/2 1/2 D = −2Γ ′′ 1/2 1/2 (JT Γ′ J + Γ′′ )−1 JT Γ′ These matrices can also be printed in G AUSSIAN with the keyword PrtMat in the ReadFCHT section (with the respective values 3. two dummy vectors. ′′ v v vN ∂Uv ∂U11 ∂U22 ∂UN ′′ ′′ ′′ and ∂ v1 ∂ v2 ∂ vN ∂v ′ = ′ ′ . .
4] selects the transitions which must be taken into account. it is possible to express any overlap integral v ′  v ′′ with respect to 0′  0′′ . an a priori scheme [3. This method relies on a categorization of the latter with respect to the number of simultaneously excited modes in the ﬁnal state. only the last recursive equation is used without the last term in the righthand side: 0′  v ′′ = + j=1 j=i 1 Di 0′  v ′′ − 1′′ + i 2vi′′ N 2(vi′′ − 1) Cii 0′  v ′′ − 2′′ i (26) ′′ 2vj Cij 0′  v ′′ − 1′′ − 1′′ i j A priori evaluation of the transition intensities Using the recursive eqs. 24 and 25. most of them correspond to transtions of negligible intensity. which is calculated exactly. setting v ′ = v ′′ = 0. 21 can be written. is to differentiate once by Ti or Ui and the result by each Tj and Uj once.In addition. eq. 7 . In the current version in G AUSSIAN. v v ′ ′′ = 2 2 v !v ! v ′ v ′′ ′ ′′ −1/2 ∂v ∂v 0′  0′′ ∂Tv ′ ∂Uv ′′ (23) ′ ′′ × exp UT CU + DT U + TT AT + BT T + UT ET T=U=0 This equation is the starting point to generate two recursive formulae depending on the initial differentiation. The procedure. with j running from 1 to N . Although. As a consequence. with respect to Ti or Ui . In G AUSSIAN. The procedure is straightforward so only the results are presented here: v ′  v ′′ = 1 Bi v ′ − 1′  v ′′ + i ′ 2vi N 2(vi′ − 1) Aii v ′ − 2′  v ′′ i N ′ vj + j=1 j=i ′ 2vj Aij v ′ − 1′ − 1′  v ′′ + i j j=1 2 Eji v ′ − 1′  v ′′ − 1′′ i j (24) and v ′  v ′′ = 1 Di v ′  v ′′ − 1′′ + i 2vi′′ N 2(vi′′ − 1) Cii v ′  v ′′ − 2′′ i N + j=1 j=i ′′ 2vj Cij v  v − ′ ′′ ′′ 1i − 1′′ j + j=1 ′ vj 2 Eij v ′ − 1′  v ′′ − 1′′ j i (25) with the ﬁrst equation corresponding to an initial differentiation by Ti and the second one to Ui . all evaluated transitions start from the vibrational ground state of the initial electronic state (T=0). 21 the overlap integral between the vibrational ground states: 0′  0′′ = 2N/2 det Γ′ Γ′′ 1/2 det(J) det JT Γ′ J + Γ′′ 1 1 × exp − KT Γ′ K + KT Γ′ J(JT Γ′ J + Γ′′ )−1 JT Γ′ K 2 2 1/4 (22) Hence. we obtain from eq. there is in principle an inﬁnite number of combinations to take into account. using the Leibniz product rule.
vi′′ ) = ∂µif ∂Q′′ i h ¯ ′′ 2ωi 2 vi′′ 0 0 + ′ ′′ vi′′ − 1′′ i + vi′′ +1 0 0+ ′ vi′′ + 1′′ i (28) 0 Finally. a similar procedure is ′′ H performed with HC1 and the condition HC1 (k. It contains all combinations of modes i and j but only considering the cases of an equal ′′ number of quanta for both modes (vi′′ = vj ): ′′ FC2 (i. FC2 and HC1 . To perform this prescreening. vi′′ = vj ) = ′′ 0′  0′′ + vi′′ + vj 2 − FC1 (i. calculations are carried out for class C1 and then class C2 . First. vi′′ ) ≥ ǫ1 for the ﬁrst max max set and FC2 (i. the max max corresponding number of integrals to calculate is roughly estimated. as NI = N Cn × v ′′ n . The second interest lies in the information provided by the reference data they provide. The advantages of using the overlap integrals of these classes are twofold. Depending on the approximation of the electronic transition dipole moment. and the keywords MaxC2 max . vi′′ ) 0′  0′′ 2 (29) From the previous description. an additional limit. j. The evaluation method is initially called to set the maximum number of quanta vi′′ to process for each mode i. A good compromise between resources usage and precision of the spectrum is set by default max = 108 ). In case of HT or FCHT calculations. respectively. The ﬁrst one is that these integrals are computationally cheap and are generated quickly even in the case of large molecules. NI is higher than the allowed limit NI . vi′′ ) = 1 Di 0′  0′′ + vi′′ − 1′′ + i 2vi′′ 2 2(vi′′ − 1) Cii 0′  0′′ + vi′′ − 2′′ i (27) where the he factors Cii and Di give respectively information on the effect of the shifts in equilibrium positions and the frequencies on the overlap integrals of overtone. ǫ1 and ǫ2 . is obtained in class 2. The highest max of the maximum quantum numbers deﬁned previously is chosen as vi′′ . FCHT and HT calculations. these are done in two steps. the overlap integrals in classes 1 and 2 are used as reference data to evaluate those to compute in each “higher” class. vi′′ ) × FC1 (j.called classes. a third threshold ǫH for HC1 is also set. these are set manually. respectively 1 viC1 and viC2 . which represents the maximum number of integrals to compute in a given class is set. Two thresholds. 2 or 3 sets of reference data are used for the prescreening. This number controls roughly the computational cost of the overall simulation. max max NI . FC or FCHT/HT. a last set FC2 . The ﬁrst set FC1 is deﬁned during the calculation of the transtions from class 1 and is used for FC. a problem arises to deﬁne the dimensions of the arrays FC1 . used for all calculations. For instance. C1 = 20 for class 1 and C2 = 13 for class 2. are met. 0′  0′′ . Practically. v ′  0′′ + vi′′ and class 0 contains the overlap integral between the vibrational ground states. This parameter can be modiﬁed in G AUSSIAN with the keyword MaxInt given in the ReadFCHT (NI section (see the keywords list for an explanation of the syntax). which stores the square of the pure HerzbergTeller contribution for a given mode i and the corresponding transition 0′  0′′ + vi′′ : HC1 (i. Since max calculations of the FranckCondon integrals in these classes are computationally cheap. is considered. max where N Cn represents the number of combinations of the n excited oscillators and v ′′ is the arithmetic mean of max max the N maximum quantum numbers. two maximum quantum numbers. In case of FCHT or HT calculations. vi′′ ) ≥ ǫ2 with j = i for the second set. 8 . a second set of data is extracted from class 1. but at the risk of a loss in accuracy of the generated spectrum if it is set too low. for a given class Cn . HC1 . a relatively high limit. These values can be max set manually in the ReadFCHT section with the keywords MaxC1 (or MaxOvr) for C1 . and gives information about the Duschinsky mixing of the normal modes. For FCHT/HT calculations. (or MaxCmb) for C2 The procedure to generate a vibronic spectrum is as follows. Once the set v ′′ has been deﬁned. vk ) ≥ ǫ1 to obtain the maximum quantum number viH . increasing the number of excited modes in the ﬁnal state. each class being calculated one after the other. chosen max max to work in most common cases. Based on this division. For class C3 and above. Its elements are deﬁned as: FC1 (i. For each mode i. class 1 (C1 ) represents all transitions to ﬁnal vibrational states with a single excited mode i. and more precisely the maximum quantum numbers vi′′ for classes C1 and C2 . j. and more precisely on the vibrational progression of mode i. are deﬁned for the sets of data FC1 and FC2 . If the number of integrals to compute. are obtained by decreasing the number of quanta vi′′ until the conditions FC1 (i.
A simple solution would be to develop µif in a Taylor series about the equilibrium geometry of the initial state. tot is rather straightforward to evaluate: The ﬁrst analytic limit. ρ′ is the Boltzmann population of each initial state. while the equality µif = µif (Q′ ) = µif (Q′′ ) is true. two analytic limits are deﬁned depending on the state of reference. and eq. max Evaluating the reliability of the prescreening with the sum rules To check the reliability of the prescreening method. 5. the intensity I tot can be written: I tot = v′ ρ′ v ′  µif · µif  v ′ (31) In case of FC calculations. tot IQ′ = µif (Q′ ) + 0 v′ 2 N ρ′ k=1 ∂µif (τ ) ∂Q′ k 2 0 h ¯ ′ ′ (2vk + 1) 2ωk (34) tot In the case of IQ′′ . When the condition NI ≤ NI max computed up to the chosen maximum number of quanta vi′′ for each mode. this is generally not the case when considering the Taylor series around each equilibrium geometry. The sum of all transition intensities is given by. However. Considering the Taylor expansion of the electronic transition dipole moment given in eq. where µif = µif (Q′′ ). As a consequence. the total intensity calculated after each class is checked with the total intensity expected using analytic sum rules. IQ′ N tot IQ′ = v′ ρ′ v ′  µif (Q′ ) + 0 k=1 2 ∂µif ∂Q′ k 2 Q′  v ′ k 0 2 (33) Using the annihilation and creation operators. eq. 31. 31 can be written: 0 ′′ I tot = µif (Q0 ) 2 v′ ρ′ v ′  v ′ = µif (Q′′ ) 0 2 (32) In the framework of the HerzbergTeller approximation of the electronic transition dipole moment (FCHT and HT calculations). 5. However. the development of µif in the Taylor series about the equilibrium geometry of the ﬁnal state is not immediate because the annihilation and creation operators obtained this way act on the quantum states of the ﬁnal state and not on the initial state. the analytic limit is given by the formula. it is straightforward to see that annihilation and creation operators will be needed to obtain the sum rules. all transition dipole moment integrals are numbers v ′′ is reestimated. Expanding the square in the previous equation and accounting for the orthonormality of the vibrational wave functions. I tot = ′ ρ′ ′′ Ψ′  µ  Ψ′′ 2 ≈ v′ ρ′ v ′′ v ′  µif  v ′′ 2 (30) where the ﬁrst sum symbol represents the summation over all possible vibrational initial states and the second one the ensemble of all ﬁnal states.the thresholds ǫ1 and ǫ2 (and ǫH for FCHT and HT calculations) are increased and the set of maximum quantum 1 max is fulﬁlled. the computation of I tot is more involved. additional steps are needed to evaluate the analytic limit: N k=1 N tot IQ′ = v′ ρ′ v ′  µif (Q′′ ) + 0 ρ v  v′ ′ ′ 2 ∂µif ∂Q′′ k ∂µif ∂Q′′ k 2 Q′′  v ′ k 0 N 2 2 (35)  v′ = µif (Q′′ ) 0 + k=1 J 0 l=1 T Q′ kl l + J T kl Kl (36) 9 . with respect to our previous deﬁnition in eq. tot tot IQ′ for the initial state and IQ′′ for the ﬁnal state.
tot tot The choice of IQ′ or IQ′′ in G AUSSIAN depends on the available data. suitable for dipoleforbidden transik=1 k k tions or to show the contribution of the HerzbergTeller approximation to the spectrum. the reference is IQ′ . G AUSSIAN will need the checkpoint ﬁle containing the data of the ﬁnal state.z v ′ N k=1 2 ρ′ N N ∂µif (τ ) ∂Q′′ k J 0 l=1 N T kl m=1 N ∂µif (τ ) ∂Q′′ m J T JT 0 h ¯ ml 2ω ′ l (2vl′ + 1) (37) −2µif (Q′′ . z) is explicitly given. This ﬁle must be given after the standard input (in general. the temperature is not yet taken into account. the analytic sum chosen as a reference to evaluate the state is Q if if 0 tot tot convergence of the spectrum is IQ′′ . Additionally. suitable for fullyallowed transitions 0 • FCHT: zeroth. the generation of a vibrationallyresolved electronic spectrum in G AUSSIAN requires a single keyword representing the terms of the Taylor series given in eq. τ ) 0 k=1 N ∂µif (τ ) ∂Q′′ k N + k=1 ∂µif (τ ) ∂Q′′ k 0 l=1 N m=1 kl Kl N JT 0 l=1 K kl l ∂µif (τ ) ∂Q′′ m JT 0 n=1 mn Kn where the summation over the Cartesian coordinates (x. the data for the initial state being taken from the current calculation. two G AUSSIAN jobs are required.y. so the relation used in practice is: 2 0′  µif  v ′′ spectrum progression = (39) Ia 3 Quick start In its most concise form. • FC: zerothorder term of the Taylor series µif = µif (Q′′ ) . below the molecule speciﬁcation). suitable • HT: ﬁrstorder term of the Taylor series µif = N (∂µif /∂Q′′ )Q′′ . 10 .where the inverse of the Duschinsky transformation given in eq. assuming the structures of the initial and ﬁnal states are already optimized: 1. Calculation of the frequencies for the initial state followed by the generation of the spectrum. 5 that must be taken into account. In this case. I tot or I tot for FCHT/HT calculations) is used to calculate The chosen analytic limit. tot After using the operators of the second quantization. a (I tot for FC calculations. y. I Q′ Q′′ the spectrum convergence (called in the G AUSSIAN output the spectrum progression) with the following relation: spectrum progression = v′ ρ′ v ′′ v ′  µif  v ′′ Ia 2 (38) In the current implementation of G AUSSIAN. IQ′′ is given by the relation: tot ′′ IQ′′ = µif (Q0 ) + τ =x. The ﬁrst one is to simulate the latter as soon as the frequencies of the initial state have been calculated.and ﬁrstorder terms of the Taylor series µif = µif (Q′′ ) + 0 for most cases spanning from fullyallowed to dipoleforbidden transitions N ′′ ′′ k=1 (∂µif /∂Qk )Qk . Hence. 14 has been used to express Q′′ with respect to Q′ . In case of emission. Two methods can be distinguished to generate the vibrationallyresolved electronic spectra. so µ (Q′′ ) and ∂µ /∂Q′′ are known. Calculation of the frequencies for the ﬁnal state 2. the excited ′′ . In the case of absorption.
HT is given in Frequency as follows (the example below is limited to the case of the FranckCondon approximation): Link 0 Commands Route section (# lines) with Frequency=(FC. As a consequence. this approach is particularly interesting when investigating the best settings to generate an accurate electronic spectrum. The input ﬁles for the ﬁrst two steps are classical ones to compute frequencies with the keyword SaveNM used in Frequency. it is also more ﬂexible as G AUSSIAN works as a standalone program dedicated to the simulation of the electronic spectra.SaveNM) NoSymm Title section Molecule speciﬁcation Name of the checkpoint ﬁle generated in step 1 In the example above. Generation of the electronic spectra The order in which the ﬁrst two steps are performed is not important and they can be done simultaneously. Schematically. FCHT. Basically. using the parameters described in the section below. two additional keywords are used.SaveNM) NoSymm Name of the checkpoint ﬁle generated in step 2 The options Geometry=AllCheck and Frequency=ReadFC are described in the G AUSSIAN manual. ﬁrst the calculation of the frequencies and then the generation of the spectrum. this gives the following procedure: 1. the keywords FC. As mentioned before. they let us extract all necessary data from the checkpoint ﬁle given in the line starting by %Chk= without the need to perform long calculations before the procedure to generate the spectrum is called. it is not well suited when diverse parameters must be tried for the generation of the spectrum. Calculation of the frequencies for the initial state 2. This option is necessary to deal with QM/MM calculations or when dealing with frozen atoms to extract correctly the normal modes and frequencies. Calculation of the frequencies for the ﬁnal state 3. A second way of using G AUSSIAN is through a 3steps procedure where the last step of the previous method is broken down in two separate steps. it is advisable to use it every time when computing the frequencies for both states and avoid possible issues caused by the impossibility of G AUSSIAN to recompute correctly the eigenvalues and eigenvectors of the Hessian matrix.In the input ﬁle for the second step. The input ﬁle for the last step is as follows: Link 0 Commands %Chk=Name of the checkpoint ﬁle generated in step 1 #P Geometry=AllCheck Frequency=(ReadFC. While not mandatory. We will however consider this sequence is respected in the following description While this method seems more complex. 11 . Since this method requires the computation of frequencies each time a spectrum must be generated. SaveNM will make G AUSSIAN save the frequencies and normal modes in the checkpoint ﬁle.FC.
respectively. As explained in the description of the FranckCondon principle. the output will be similar and structured as follows. Next. not possible. after a predetermined number of iterations. Although the latter approach (which is the default) should be more stable and direct. using Euler angles [11–13] or quaternions [14. Data for final state taken from checkpoint file "checkpoint ﬁle of step 1" Normal modes recovered from file. of the electronic transition dipole moment: FC Type of transition requested: ONEPHOTON ABSORPTION The output presented above is an example showing the case of an absorption spectrum with the electronic transition dipole moment considered as constant during the transition. Initial state structure is set in Eckart orientation. their coupling for the initial electronic state can be minimized by putting the molecule in the Eckart orientation (origin in the mass center and Cartesian axes along the principal inertia moments) using the standard G AUSSIAN orientation for the ordering of Cartesian axes. so that. the output will be: Data for initial state taken from current calculation.15]. the program shifts to Euler angles. Two options are next possible for the ﬁnal electronic state. namely to use its own Eckart orientation. The last line is followed by the geometry of the system in both states after reorientation.Description of the output Whatever the chosen procedure. The actual calculation is then presented: 12 . the approximation of the electronic transition dipole moment and the type of transition: Approx. respectively. the molecule in the ﬁnal electronic state is ﬁrstly rotated using the same rotation matrix of the reference state and next a new rotation matrix is computed in order to minimize the angular momentum between initial and ﬁnal structure NA Mii X′ ∧ X′′ i i i=1 (40) where M is the diagonal matrix of the atomic masses. The second one is the default because it minimizes the contribution of rotations to the shift vector and the Duschinski matrix. Although rigorous separation between rotations and vibrations is. G AUSSIAN then describes the procedure of extraction of the data from the sources. The block in the output related to the generation of the spectrum starts with the following output: ********************************************************************** Generation of the FranckCondon spectrum ********************************************************************** General information is then given on the type of calculation. or to minimize the angular momentum between initial and ﬁnal structures. the calculation of the vibronic spectra requires the minimization of nuclear displacements during the transition. Passedin normal modes used. There are two options to build the rotation matrix. there are cases in which it fails. In the case of our quick start procedure. Final state structure is superposed to it. X′ and X′′ are the triplets of Cartesian coordinates for the i i nucleus i in the initial and ﬁnal states. of course. This two step procedure [10] allows to avoid numerical problems when the geometries and/or starting orientations of initial and ﬁnal states are strongly different.
it can be not well suited for particular cases or poorly adapted to speciﬁc requirements from the user.. The resulting G AUSSIAN input is structured as follows: 13 .....xxxxExxx .xxxxxxDxxx 4 List of options While the default behavior of G AUSSIAN is set to give satisfactory results in most cases.Overlap integrals computation Energy of the 00 transition: Calculated value cmˆ(1) Notes about the overlap integrals description: ....Intensity is the line intensity (absolute value) A list of the most intense transitions is then printed.... A number of options exist to extensively parameterize the calculations and provide a satisfactory analysis of the case of interest. the spectrum generated by G AUSSIAN is printed: ++  Final Spectrum  ++ Axis X = Energy (in cmˆ1) Axis Y = Intensity (in arbitrary units) xxxxx.xx% Finally...TDMIˆ2 is the square of the transition dipole moment integral . The ﬁrst line represents the initial state and the second line the ﬁnal state. They are listed by incrementing class.. The general format is: Initial State: <0 Final State: xˆx.xxxxExxx.....xxxx x. These options need to be given in a speciﬁc section referred to as the “ReadFCHT section”.. The character x given above represents a digit or a sign... 0′  0′′ ..xˆx> DeltaE = x... Intensity = x..xxxx  TDMIˆ2 = x. The third line contains the energy of the transition with respect to the energy of the transition between the vibrational ground state. This section lies below the standard G AUSSIAN input and is activated by adding the keyword “ReadFCHT” in the option Frequency....... the convergence of the spectrum is printed: ++ Spectrum progression: xx.....DeltaE is the relative energy of the transition (wrt 00) . and the intensity of the corresponding spectrum line..... the value  v ′  µif  v ′′ 2 . Once a class has been treated.
two keywords in the same “line” are equivalent (ex: ABS and ABSORPTION). This approximation is more general than FC and works on diverse cases. The electronic transition dipole moment is developped in a Taylor series about the equilibrium geometry of the ﬁnal state up to the ﬁrstorder term included. The simulated vibronic spectrum corresponds to a onephoton emission transition. All keywords given in the same block of lines correspond to the same option and are mutually exclusive (ex: FC. FCHT and HT). The options available for the simulation of vibronic spectra using the FranckCondon principle are listed in the table below. This approximation is generally well suited for fullyallowed transition. To make the reading of the latter easier. they should be used carefully. Data for the initial state are taken from the G AUSSIAN output ﬁle provided below the ReadFCHT section. blocks are deﬁned between two consecutive horizontal black lines. it is highly advisable to avoid their use by default as they will bypass protections of G AUSSIAN regarding the soundness of the calculations. Note: Regarding the last group of options dealing with forced calculations. from fullyallowed to dipoleforbidden transitions. Data for the ﬁnal state are taken from the current G AUSSIAN job. In general. (Default) The simulated vibronic spectrum corresponds to a onephoton absorption transition. Keyword FC Values None Description General parameters of the calculations (Default) The electronic dipole moment is assumed constant during the transition. the lines are differentiated by alternating backgrounds of different colors. Additionally. FCHT None HT None ABSORPTION ABS EMISSION EMI None None 14 . Data for the initial state are taken from the checkpoint ﬁle provided below the ReadFCHT section.Link 0 Commands Route section (# lines) with Frequency=(ReadFCHT) Title section Molecule speciﬁcation Optional additional sections used by links called before l716 ReadFCHT section The description of the different sections above the ReadFCHT section can be found in the G AUSSIAN 09 manual and is outside the scope of this document. only the last one is taken into account and the others are discarded. As a consequence. organized by functions. Following this scheme. 5). Sources of input data CALC1 CHK1 OUT1 CALC2 None None None None (Default) Data for the initial state are taken from the current G AUSSIAN job. Only the linear variation of the electronic transition dipole moment with the normal coordinates of the ﬁnal state is taken into account (ﬁrstorder term of the Taylor series given in eq. when several keywords related to the same option are given.
Sharp and Rosenstock matrix C 6. 14. Please note that. Sharp and Rosenstock vector D 7. Ex: PRTMAT=12 corresponds to printing the Duschinsky matrix and shift vector. A digit is assigned to each matrix as follows: 1. (Default) Uses the correct Duschinsky matrix to perform the calculations. JT is printed. shift vector K 3. Sharp and Rosenstock matrix A 4. The frequencies are expected in cm−1 . Such value is expected in Hartree and is not taken in account if null. See ref.0 (= Off) SclVec None JDusch JIdent None None Parameterization of the G AUSSIAN output PRTMAT 0 (= Off) ALLSPECTRA PRTINT None 0. energy. [16] for more details on its behavior. Sharp and Rosenstock matrix E The digits corresponding to the matrices to be printed are placed side by side to form a number that is given as the value of PRTMAT. A modespeciﬁc scaling algorithm based on the Duschinsky matrix is used to compute new frequencies for the ﬁnal state using the differences between the calculated frequencies for the initial states and usergiven ones listed below the ReadFCHT section. Chooses the electronic state from which the data relative to the electronic transition dipole moments and the derivatives are taken.01 15 .Keyword CHK2 OUT2 NSTATE Values None None 1 Description (Default) Data for the ﬁnal state are taken from the checkpoint ﬁle provided below the ReadFCHT section. Sharp and Rosenstock vector B 5. Duschinsky matrix J. intensity) of the transitions which have an intensity ( v ′  µif  v ′′ 2 ) above or equal to 1% of the total analytic limit. Setting of the spectrum layout Usergiven input data or modiﬁcation options InpDEner 0. Replaces the calculated difference of energy between both electronic states involved in the transition by the value given by the user. Uses an identity matrix instead of the Duschinsky matrix. 2. with respect to eq. Prints the Sharp and Rosenstock matrices or the Duschinsky matrices and vectors. Prints data (assignment. In this case the modemixing is ignored. total spectrum. Data for the ﬁnal state are taken from the G AUSSIAN output ﬁle provided below the ReadFCHT section. Prints the spectra corresponding to each class in addition to the ﬁnal.
The value is normally given relative to the energy of the transition between both vibrational ground states. Calculations can end before if there are not enough excited modes or DELTASP is also deﬁned and the condition imposed by the latter is met before.0 Description Sets (in cm−1 ) the lower bound of the spectrum. The value is normally given relative to the energy of the transition between both vibrational ground states. G AUSSIAN expects the lower and upper bound of the spectrum to be given in absolute values (not relative to the 00 transition). then the calculations end. analytic formulae are used when available for these classes. This keyword should be used together with both SPECMIN and SPECMAX to avoid an unexpected behavior. max Sets the maximum number of integrals (NI . Sets the maximum quantum number to consider for each mode involved max in the combination bands in C2 (C2 ). Sets the maximum class to consider. Forces the printing of the ﬁnal spectrum even if the total progression is low (below 50%). Forcing calculations4 Forces the calculation of the FranckCondon integrals even if the overlap integral between the vibrational ground states of the initial and ﬁnal states is very low ( 0′  0′′ 2 < 10−4 ).Keyword SPECMIN Values 1000. It is noteworthy that a very high resolution (given by a small value of SPECRES) can greatly hamper the computational speed of the spectrum generation. Sets a condition on the spectrum convergence.0 NORELI00 None SPECRES 8.0 SPECHWHM 135. A large value of SPECHWHM coupled to a small value of SPECRES can cause a steep increase of the computational times. Resolution of the spectrum given by the difference of energy between two contiguous measuring points (in cm−1 ). Sets the HalfWidth at HalfMaximum (in cm−1 ) for the convolution of the spectrum using a Gaussian distribution. expressed in million) to compute for each class above C2 . By default.0 SPECMAX +8000. each optional block of data (“SclVec” and “Sources”) being terminated by a blank line: 4 Warning: The keywords describe in this section should be used with care as they might lead to results whose reliability is unpredictable 16 . Sets the maximum quantum number that has to be considered for each max mode of C1 (C1 ). Deactivates the usage of analytic formulae to compute the overlap integrals in classes C1 and C2 .0 ForceFCCalc None ForcePrtSpectrum None The structure of the G AUSSIAN input ﬁle starting from the ReadFCHT section is as follows. Using this keyword. If the spectrum progression with respect to the total intensity between two consecutive classes is below DELTASP (in absolute value). Sets (in cm−1 ) the upper bound of the spectrum. Modiﬁcation of the behavior of the a priori scheme to chose the most relevant transition MAXOVR MAXC1 MAXCMB MAXC2 MAXINT NOINTAN 20 13 100 None Termination criteria for the spectrum generation MAXBANDS 7 DELTASP 0.
5 SF6_anion_freq. When generating the photodetachment spectrum of SF6 with the standard parameter.SaveNM. The G AUSSIAN inputs presented here are based on the 3steps usage of G AUSSIAN.chk max C1 is set to a safe. Photodetachment spectrum of SF− : parameterizing the prescreening method 6 In the photodetachment spectrum of SF− .‘‘Sources’’ block rent G AUSSIAN job) Name of the ﬁle containing the data for the ﬁnal state (if different from the current G AUSSIAN job) [blank line] By default.SaveNM. an insufﬁcient value of MAXC1 is set and only a partial spectrum is obtained. where the last step is dedicated to the generation of the spectrum. As a consequence.ReadFCHT) NoSymm PRTMAT=12 MAXC1=100 MAXBANDS=4 SPECHWHM=0. G AUSSIAN will ﬁnd that it does not need to go up to class 7 and will safely stop the calculations. SPECRES=1.ReadFCHT section [blank line] ‘‘SclVec’’ block Usergiven frequencies for the initial state (necessary for SclVec) [blank line] Name of the ﬁle containing the data for the initial state (if different from the cur. anisole_S1. we set manually the correct limit. only the name of the checkpoint ﬁle containing the data of the ﬁnal state needs to be given after the ReadFCHT section. a signiﬁcant elongation of the SF bond upon electron attachment is found. 2 in ref [18]). it is necessary to modify the default values of the parameters corresponding to the spectrum layout.FC.chk #P Geom=AllCheck Freq=(ReadFC.ReadFCHT) NoSymm PRTMAT=12 NORELI00 SPECMIN=37900 SPECMAX=42000 SPECHWHM=1. This is done with the following input %Chk=anisole_S0. the following input ﬁle is used for the generation of the complete spectrum: %Chk=SF6_neutral_freq.chk 17 . the potential curves of the normal mode corresponding to the SF symmetric stretching are no− ticeably displaced (see Fig. high value since the cost of the prescreening is cheap. When performing the calculation. Here. 5 Some practical examples The examples described here are taken from reference [17] and shows the parameters used in the ReadFCHT section to carry out the calculations. S1 ← S0 absorption spectrum of Anisole: parameterizing the spectrum layout To compare the theoretical spectrum obtained with G AUSSIAN and the experimental REMPI spectrum. 6 As a consequence.chk #P Geom=AllCheck Freq=(ReadFC.FC.
52 417.75 1177. 18 . their origin as well as possible workarounds or leads that should be investigated to solve them.60 994.32 1082.93 757.61 anisole_S1.95 981.62 2902.47 3047.04 3068.55 1465.ReadFCHT) NoSymm PRTMAT=12 NORELI00 SPECMIN=37900 SPECMAX=42000 SPECHWHM=1. the scaling vector for the excited state α′′ is deduced from α′ with the relation.62 1018. However.61 883.21 784.The absolute values of the spectrum bounds are given here and a very ﬁne spectrum is requested.75 1305.39 200.45 1467. the latter are there to draw the attention of the user on potential issues.51 2993.75 1146. excited state with the timedependent density functional theory (TDDFT) computations.76 1601. Hence. While the former will result in a termination of the calculations.94 3042. To correct this.Cannot extract data for both states from the current calculations This error is due to the fact that G AUSSIAN attempts to extract all data from the current job. we present a brief overview of the most common error and warning messages.69 1582. SclVec 86.FC. ′ is calculated: a scaling vector α ′ ′ ′ αi = ωanh /ωharm Using the square elements of the Duschinsky matrix.74 696.61 1479. SPECRES=1.46 437.63 1040.80 1454.57 510. anharmonic frequencies had to be used. Depending on the origin of the problem found.40 2869. In this section.53 3077.59 257.chk G AUSSIAN then corrects the harmonic frequencies of the excited state with a modespeciﬁc scaling to account for ′ the anharmonicity. they could not be straightforwardly obtained for the ﬁnal. an energy shift was observed for several peaks.73 1494. 6 Description of the errors reported by G AUSSIAN Several controls are performed in G AUSSIAN to check the validity of the calculations.70 1164. Errors . calculations can be aborted with an error or a simple warning can be issued.chk #P Geom=AllCheck Freq=(ReadFC.42 1177. Using the harmonic frequencies present in the checkpoint (ω ′ harm ) and the usergiven data (ω anh ).57 3006. The anharmonic frequencies calculated for the ground state [19] were used as input as follows: %Chk=anisole_S0.86 554.32 811.38 252.SaveNM.26 623. Although the spectrum layout obtained this way is very similar to the experimental one.54 1336. with the frequencies calculated at the harmonic level. the modespeciﬁc scaling scheme [16] implemented in G AUSSIAN and available with the keyword SclVec was used. N ′′ αj = i=1 ′ Jij 2 αi The new anharmonic frequencies ω ′′ anh are then calculated as: ′′ ′′ ′′ ωanh = αi ωharm G AUSSIAN prints in output the scaling vectors α′ and α′′ as well as the frequencies that will be used in each state for the calculation of the vibonic spectrum.40 1238.10 958.
G AUSSIAN will have set the current calculation for the ﬁnal state. the FranckCondon principle.0D6. Bloino.D3 for example will print the assignment of all integrals which contribute to at least 0. Calc. warnings should have been issued during the calculations: Warning: insufﬁcient num. . Improta. Another indicator of this problem is the Duschinsky matrix (which can be displayed with the option “PRTMAT=1” in the ReadFCHT section) that shows the projection of the normal modes of one state on those of the other state.WARNING: Charge (or Multiplicity) is different between initial and ﬁnal states. The Journal of Chemical Physics 126. This error is often related to the same reasons as the previous one. 084509 (2007). G AUSSIAN found that the condition FC1 (i.It is likely that CALC1 has been given without setting the source of data for the ﬁnal state. 858 (1928). This can happen when one of the structures is planar in one electronic state and not planar in the other electronic state. Transactions of the Faraday Society 21. please use the keyword FORCEPRTSPECTRUM. Condon. Reset to 1. If the calculations must be carried anyway. C1 max ) ≥ ǫ1 was true for the normal mode i. A. this error can be bypassed with the keyword ForcedFCCalc. The ﬁrst one is to increase MAXBANDS which correspond to the highest class to be treated. . is unsuitable for the case of interest. R. . [3] F.Warning: insufﬁcient num. If this it is not the case. Physical Review 32. that is to say that many normal coordinates of the ﬁnal state are expressed by a combination of a rather large number of normal modes of the initial state. [2] E.1% to the total intensity. If this is the case. PRTINT is given as a fraction of the total analytic sum. To print the spectrum nevertheless. This is a typical issue when the equilibrium geometry of the initial and ﬁnal states are noticeably different. J. Santoro. Improta. MAXC1=20). in the data ﬁles This error is raised if a FCHT or HT calculation is requested and G AUSSIAN cannot use the transition electronic dipole moment and its derivatives that were found in the source ﬁles. For this kind of calculation. and V. Finally. 19 . then the spectrum convergence will be limited. [4] F. Lami. Be careful that it can cause a very verbose output of Gaussian. the transition is generally fullyallowed and the FC approximation should be sufﬁcient. Bloino. If it has been set very low. Barone. the problem may be caused by too low number of calculated transitions. the Duschinsky matrix is rather diffuse. R. cannot be done out with the trans. Such a condition means that the parameter MAXC1 must be set with a higher value that the current one (by default.ERROR: The ﬁnal spectrum progression is too low and the resulting spectrum may be unreliable. that is to say that the FranckCondon principle can be unsuitable to the case of interest. Barone. of quanta for mode i. References [1] J. A. Setting a very low value of PRTINT might cause the generation of a very large output ﬁle. Several options may resolve this problem. J. By default. 224311 (2008). In this case. 536 (1926). dip. However. Other possibility is that the values of MAXC1/MAXOVR and/or MAXC2/MAXCBI are set too low. Franck.ERROR: The FranckCondon factor corresponding to the overlap integral between both vibrational ground states is too small: <0’0">ˆ2 = x This error indicates that it is very likely that the underlying theory used to generate the spectrum. and V. setting PRTINT=1. Lami. mom. of quanta for mode i. . The Journal of Chemical Physics 128. please note that the resulting spectrum will be likely unreliable and the corresponding calculations should be considered as tests. this error can also be caused by a low number of transitions to compute in each class (MAXINT). Warnings . Santoro. As a consequence.WARNING: Value for PRTINT is too low.
Acta Physicochimica URSS 7. Eckart. 3778 (1974). Bopp. C. 1214 (2007). M. u [7] F. A. Crescenzi. [9] P. [11] S. Van der Veken. B. Physical Review 47. and M. and Y. Biczysko. Ruhoff. C. G. A. Rosenstock. J. [16] J. Herman. Bloino. Chemical Physics 186. and V. Barone. The Journal of Chemical Physics 128. 355 (1994). [12] W. Ruf. Chang. [15] G. Lineberger. [13] C.[5] C. The Journal of Chemical Physics 88. [10] B. Roscioli. Miller. A. 540 (2009). Johnson. and W. Kneller. and F. Journal of the American Chemical Society 96. E. Barone. Teller. 552 (1935). Bloino. Herzberg and E. 6298 (1988). Molecular Simulation 7. Santoro. Journal of Chemical Theory and Computation 5. Ehrenson. 20 . Wren. Miller. 481 (1989). M. [8] T. Sharp and H. [19] V. Biczysko.Abteilung B 21. M. Journal of Physical Chemistry A 111. O. S. Theoretical Chemistry Accounts 75. W. 113 (1991). Kneller. Zeitschrift f¨ r Physikalische Chemie . Theochem 91. 244105 (2008). J. 387 (1983). 551 (1937). M. M. The Journal of Chemical Physics 122. R. [6] G. Barone. The Journal of Chemical Physics 41. Viggiano. S. Zhixing. Duschinsky. Pieters. The Journal of Chemical Physics 89. 3453 (1964). 2709 (1991). [17] V. [18] J. 410 (1933). 014108 (2005). [14] G. T. Villano. M. T.
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