Natural transition orbitals

Richard L. Martin

Citation: J. Chem. Phys. 118, 4775 (2003); doi: 10.1063/1.1558471

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JOURNAL OF CHEMICAL PHYSICS VOLUME 118, NUMBER 11 15 MARCH 2003

COMMUNICATIONS

Natural transition orbitals

Richard L. Martin
Theoretical Division, MS B268, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
共Received 13 January 2003; accepted 15 January 2003兲
A means of finding a compact orbital representation for the electronic transition density matrix is
described. The technique utilizes the corresponding orbital transformation of Amos and Hall and
allows a dramatic simplification in the qualitative description of an electronic transition. © 2003
American Institute of Physics. 关DOI: 10.1063/1.1558471兴

The description of electronically excited states is often
couched in terms of excitation amplitudes based on a set of
ground state orbitals. For example, in the configuration inter-
action singles 共CIS兲 approach to excited states, the many-
electron space consists of all single particle-hole excitations
共singles兲 from the ground state. In ab initio approaches uti-
lizing the Hartree–Fock ground state this is often a fairly
crude approximation, but it can be effective when used with
semi-empirical Hamiltonians.1– 4 A similar expansion is used
in linear response approaches to excited states such as the
random-phase approximation 共RPA兲. The RPA can be ap-
plied to reference states derived from either Hartree–Fock or
density functional theory 共DFT兲. The latter approximation
also goes by the name of time-dependent DFT 共TDDFT兲.5–11
It is becoming increasingly popular as it appears to be sig-
nificantly more accurate than the analogous approach applied
to Hartree–Fock reference states.3,4
The end result of such a calculation is an excitation en-
ergy and a set of coefficients describing the contribution that
each particle-hole pair makes to the excited state 共excitation
amplitudes兲. Oftentimes, there is no dominant configuration
in the list of excitation amplitudes, thereby making a
straightforward interpretation of the excited state difficult.
For the sake of having a specific example, let us consider
the CIS approximation, which is equivalent to the Tamm–
Dancoff approximation of TDDFT. The result of a self-
consistent-field 共SCF兲 calculation on the ground state is an
orthogonal set of No occupied spin orbitals, ␺ i , and a set of
Nv unoccupied spin orbitals, ␺ a⬘ . Assume that Nv ⭓No , as is
usually the case. The relevant quantity associated with the
electronic excitation is the single particle transition density
matrix T, a rectangular No ⫻Nv matrix coupling the ground
state ⌿ 0 with the excited state ⌿ ex ,
T ia ⫽ 兺␴ 具 ⌿ ex兩 c i†␴ c a ␴兩 ⌿ 0 典 . 共1兲
The index i labels occupied orbitals in the set ␺ and the
index a labels the virtuals in set ␺ ⬘ . ␴ is the spin index.
We construct two new sets of orbitals, defined by the
unitary transformations
共 ␾ 1 , ␾ 2 ,..., ␾ No 兲 ⫽ 共 ␺ 1 , ␺ 2 ,..., ␺ No 兲 U, 共2兲
and
共 ␾ ⬘1 , ␾ 2⬘ ,..., ␾ ⬘N 兲 ⫽ 共 ␺ ⬘1 , ␺ ⬘2 ,..., ␺ ⬘N 兲 V. 共3兲
v v

This is particularly unsatisfactory when attempting to deter- The matrices U and V are determined by solving the
mine the qualitative nature of an excited state. An additional eigenvalue equation
complication in the DFT case is that in principle all orbitals
in DFT but the HOMO are devoid of physical significance. TT† u i ⫽␭ i u i ,i⫽1...No 共4兲
However, chemical intuition is built on the orbital construct,
and a simple orbital interpretation of ‘‘what got excited to T† Tv i ⫽␭ ⬘i v i ,i⫽1...Nv 共5兲
where’’ is important. with
In this communication I describe an approach to this
problem which relies on finding a compact orbital represen- U⫽ 共 u 1 ,u 2 ,...,u No 兲 , 共6兲
tation for the electronic transition density matrix. By apply-
ing separate unitary transformations to the occupied and the V⫽ 共 v 1 , v 2 ,..., v Nv 兲 . 共7兲
virtual orbitals, a maximal correspondence between the ex-
cited ‘‘particle’’ and the empty ‘‘hole’’ can be obtained, with- The new orbitals ␾ and ␾ ⬘ have the following useful
out changing the physically relevant quantity, the transition properties:
density. This is accomplished using the corresponding orbital 共a兲 If the ␭ i and ␭ i⬘ are separately numbered in order of
transformation of Amos and Hall.12 This transformation has decreasing magnitude, then
been used extensively in quantum chemistry, but to my 1⭓␭ i ⬅␭ i⬘ ⭓0, i⫽1...No , 共8兲
knowledge it has not been applied in the present context
previously,13 and therefore merits a brief review. and

0021-9606/2003/118(11)/4775/3/$20.00 4775 © 2003 American Institute of Physics

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4776 J. Chem. Phys., Vol. 118, No. 11, 15 March 2003 Richard L. Martin

No

兺i ␭ i ⫽1. 共9兲

共b兲 The eigenvectors v No ⫹1 ... v Nv will have eigenvalues

zero.
共c兲 The transition density matrix expressed in terms of
the new orbitals is diagonal,
兩 关 U† TV兴 i j 兩 ⫽ 冑␭ i ␦ i j . 共10兲
Note what has been accomplished with this transforma-
tion. The No Nv transition amplitudes which previously
served to define the excitation have been reduced to a set of
No particle-hole amplitudes. With each hole in the occupied
space, one can associate a single corresponding particle in
the virtual space. The importance of a particular particle-hole
excitation to the overall transition is reflected in the associ-
ated eigenvalue ␭ i .
The application of this transformation to RPA or TDDFT
transition densities follows along the same lines. However,
due to the presence of the de-excitation operators the eigen-
N
value sum 兺 i o ␭ i will not be identically one, but will deviate
from that to the extent that the de-excitation operators are
significant. These de-excitation terms are usually small, as
witnessed by the success of the Tamm–Dancoff approxima-
tion 共which ignores them兲 in reproducing TDDFT.11 Exten-
sion to spin-unrestricted cases is straightforward, as separate
transformations may be applied to each spin index in turn,
rendering the ␣␣ and ␤␤ components of the transition den-
sity individually diagonal.
FIG. 1. 共Color兲 The dominant natural transition orbital pairs for the first
This procedure has been implemented in a local version three excited singlet states of 关 Re(bpy)(CO) 3 (4-Etpy) 兴 ⫹ . The first excited
of the GAUSSIAN 98 suite of programs14 and utilized with the state is at the top of the figure; for each state, the ‘‘hole’’ is on the left, the
TDDFT implementation of Stratmann, Scuseria and Frisch.10 ‘‘particle’’ on the right. The associated eigenvalues ␭ are 0.9962, 0.9967,
As an example of the approach we consider the excited states and 0.9809, respectively.
of a d 6 Re complex recently studied by Dattelbaum and
coworkers15 shown in Fig. 1. The molecule is the pseudo- associated hole involves significant contributions from both
octahedral Re(bipyridyl)(CO) 3 (4-ethylpyridine) ⫹ ion. The ␺ homo⫺1 and ␺ homo⫺2 . For example, from the amplitudes in
calculations utilized the LANL2 relativistic effective core Table I the second excited state is approximately described
potential for Re. The associated double-zeta basis set17 was as 0.7973 ( ␺ homo⫺2 → ␺ lumo⬘ )⫹0.5886 ( ␺ homo⫺1 → ␺ lumo).
completely uncontracted. Note, however, that when the The third excited state differs primarily in the phase of the
LANL2DZ basis is uncontracted, two nearly linearly depen- configuration mixing. This leads to one weak transition and a
dent p functions result. One function ( ␣ ⫽0.4644) was re- higher energy, more intense one. The last column reports the
tained, and one deleted ( ␣ ⫽0.4900). The 6-31G* basis set largest natural transition orbital eigenvalue, ␭ max , for each
was utilized for the ligands. A geometry optimization using state. This eigenvalue is ⭓0.98 for all the states, signifying
the B3LYP DFT approximation16 was followed by a TDDFT that even the heavily mixed second and third states can be
calculation of the lowest singlet states employing the same quite well described in terms of a dominant excitation pair
functional. accounting for over 98% of the transition. Stated another
The TDDFT calculation provides excitation energies and way, if the calculation were repeated for a specific excited
oscillator strengths to the lowest singlet states reported in state using the transition natural orbitals appropriate for it,
Table I. The lowest excitation carries little oscillator strength, the leading term would be 冑␭ max(␾max→␾max ⬘ ). This coeffi-
and is fairly cleanly described as ␺ homo→ ␺ lumo⬘ . The next cient is ⭓0.99 for all three states in their respective transition
⬘ , but the
two excited states also involve excitation into ␺ lumo natural orbital basis. Plots of the pairs are given in the Fig. 1.

TABLE I. TDDFT results for the low lying excited states in 关 (bpy)Re(CO) 3 (4-Etpy) 兴 ⫹ .

Excited State ⌬E(eV) f Description ␭ max

1 2.65 0.0031 ⬘ )
0.9894 ( ␺ homo→ ␺ lumo 0.9962
2 2.91 0.0079 ⬘ )⫹0.5886 ( ␺ homo⫺1 → ␺ lumo)
0.7973 ( ␺ homo⫺2 → ␺ lumo 0.9967
3 3.02 0.0658 ⬘ )⫹0.7642 ( ␺ homo⫺1 → ␺ lumo)
⫺0.5883 ( ␺ homo⫺2 → ␺ lumo 0.9809

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J. Chem. Phys., Vol. 118, No. 11, 15 March 2003
2
Note that all three states are metal-to-ligand charge transfer
in character, the excitation promoting an electron from an
3
orbital that is dominantly on the Re center to one that is
localized on the bipyridyl group. The three states differ only 4
in the particular d ␲ Re orbital involved.
In summary, I have described an orbital transformation 5
6
which should be quite helpful in providing a qualitative de-
scription of an electronic excitation. In addition to providing 7
a simple orbital interpretation of the excitation, all one-
electron properties associated with the transition, such as the
8
transition dipole, may be interpreted in a transparent way as
a sum over the occupied natural transition orbitals, each or-
bital being paired with a single unoccupied orbital, weighted 9
with the appropriate eigenvalue ␭.
This contribution is dedicated belatedly to Professor 10
Ernest Davidson on the occasion of his 65th birthday. I
would also like to thank Professor Davidson, and Dr. P. J.
11
Hay and Dr. S. Tretiak for helpful conversations on this 12
topic. The work was performed at Los Alamos National 13
Laboratory, operated by the University of California for the
U.S. Department of Energy under contract number W-7405-
14
ENG-36. I am grateful to the Laboratory Directed Research
and Development Program at Los Alamos for support. 15
1
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