Symmetry Groups and Quantum Dynamics of Rigid and

Non-Rigid Molecules

Alexander Alijah
Groupe de Spectrométrie Moléculaire et Atmosphérique
University of Reims, 51100 Reims - France

February 2016

Workshop on Theoretical Chemistry Mariapfarr – 1 / 64

Point Groups
Some Properties
Fundamental
approximations
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Point Groups
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 2 / 64

 Point Groups

Point Groups operation

Some Properties
Molecule ⇀
↽ Indistinguishable Molecule
Fundamental
approximations
inverse operation
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups
Operator Symmetry Element
Rotational motion Identity, Ê –
Rigid Molecules Rotation by 2π/n, Ĉn n-fold symmetry axis
Floppy Molecules
Reflection, σ̂ plane of symmetry
Non-rigid
Molecules: Single σv vertical plane
Potential Energy
Surface σh horizontal plane
Non-rigid
Molecules:
σd diagonal plane
Multiple Potential
Energy Surfaces
Rotation-reflection n-fold improper symmetry axis
Summary and or improper rotation, Ŝn
Literature
Ŝn = Ĉn σ̂h = σ̂h Ĉn
Inversion, î centre of inversion

Workshop on Theoretical Chemistry Mariapfarr – 3 / 64

 Point Groups

Point Groups
Some Properties
Rotation (BF3 ) Reflection (C6 H6 , benzene)
Fundamental
approximations
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Improper Rotation (CH4 , methane) Inversion (C2 H2 , ethene)
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 4 / 64

 Point Groups

Point Groups
Some Properties
Symmetry elements of water: point group C2v
Fundamental
approximations
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces Multiplication table: Ĉ2 ≡ Ĉ2 (z), σ̂v ≡ σ̂v (yz), σ̂v′ ≡ σ̂v (xz)
Summary and
Literature
C2v Ê Ĉ2 σ̂v σ̂v′
Ê Ê Ĉ2 σ̂v σ̂v′
Ĉ2 Ĉ2 Ê σ̂v′ σ̂v
σ̂v σ̂v σ̂v′ Ê Ĉ2
σ̂v′ σ̂v′ σ̂v Ĉ2 Ê

Workshop on Theoretical Chemistry Mariapfarr – 5 / 64

 Point Groups: Algorithm

Point Groups
Some Properties
Fundamental
approximations
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 6 / 64

 Point Groups: Representations

Point Groups Example: Water in the yz plane. If in xz plane, B1 and B2 are interchanged
Some Properties
Fundamental
approximations
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 7 / 64

 Point Groups: Normal Modes

Point Groups
Some Properties
■ Normalmodes
Fundamental
approximations
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups ■ Interpretation within the point group:
Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules: ■ character table
Multiple Potential
Energy Surfaces
Summary and
C2v Ê Ĉ2 (z) σ̂v (yz) σ̂v′ (xz)
Literature A1 1 1 1 1
A2 1 1 -1 -1
B1 1 -1 1 -1
B2 1 -1 -1 1
Γ(v1 ), Γ(v2 ) 1 1 1 1 A1
Γ(v3 ) 1 -1 -1 1 B2

Workshop on Theoretical Chemistry Mariapfarr – 8 / 64

 Point Groups: Limitations

Point Groups
Some Properties
Non-rigid molecules
Fundamental
approximations ■ large amplitude vibrations, for example H+
3
Complete Nuclear
Permutation and
■ more than one stable structure, for example NH3
Inversion (CNPI)
Groups Let us look at
Rotational motion

Rigid Molecules ■ the theoretical basis that leads to point group classification
Floppy Molecules ■ the true symmetry of the molecular Hamiltonian
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 9 / 64

 Schrödinger Equation

Point Groups
Some Properties
1. time-dependent
Fundamental  
approximations ∂
ih̄ − H(Q, q, t) Ψ(Q, q, t) = 0
Complete Nuclear
Permutation and
∂t
Inversion (CNPI)
Groups

Rotational motion
h̄2 X 2 X h̄2 2
H(Q, q) = − ∇i + ∇I + V (Q, q, t)
Rigid Molecules 2me 2MI
i I
Floppy Molecules
Non-rigid
Molecules: Single 2. time-independent if potential does not depend on t
Potential Energy
Surface
Non-rigid
[H(Q, q) − Eα ] ψα (Q, q) = 0
Molecules:
Multiple Potential ■ translational motion separable from internal motion in
Energy Surfaces
Summary and
absence of magnetic fields
Literature
[H(R, r) − Eα ] ψα (R, r) = 0
Q, q: coordinates in laboratory system; R, r: coordinates in
molecule-fixed system with axes parallel to laboratory system
■ internal Schrödinger equation not separable
■ sequence of approximations to solve it

Workshop on Theoretical Chemistry Mariapfarr – 10 / 64

 Separation of degrees of liberty

Point Groups
Some Properties
1. of nuclei and electrons: adiabatic approximation (MI >> me )
Fundamental
approximations
Complete Nuclear
ψα (R, r) = Φn (r; R) Θnα (R)
Permutation and
Inversion (CNPI)
Groups

Rotational motion
■ notion of potential energy surface
Rigid Molecules
■ minimum: concept of molecular structure
Floppy Molecules
2. of electrons: Hartree-Fock
Non-rigid
Molecules: Single Y
Potential Energy
Surface Φn (r; R) = Â φi (~ri ; R)
Non-rigid i
Molecules:
Multiple Potential
Energy Surfaces
Summary and
■ first approximation:
Literature
doesn’t describe dissociaton; ca. 2% of electronic energy
missing
■ followed by a correlation method such as CI

Workshop on Theoretical Chemistry Mariapfarr – 11 / 64

 Separation of degrees of liberty

Point Groups
Some Properties
3. of rotation and vibration
Fundamental
approximations
3N
~˙ I
~I × R
X
Complete Nuclear T = Tvib + Trot + Trot,vib ; Trot,vib = 2~
ω MI R
Permutation and
Inversion (CNPI) I =1
Groups

Rotational motion
■ Eckart conditions (reference configuration R0 )
Rigid Molecules

Floppy Molecules 3N
~ I0 × R
~I = 0
X
Non-rigid
Molecules: Single
MI R
Potential Energy I =1
Surface
Non-rigid
Molecules: 4. of vibrational modes (reference configuration R0 )
Multiple Potential
Energy Surfaces
2

1 ∂ V 
Summary and
Hvib ≈ Tvib + V0 + ∆Ri ∆Rj + · · ·
Literature
2 ∂Ri Rj R 0

■ diagonalization of Hesse matrix

■ normal modes: approximate quantum numbers
■ selection rules

Workshop on Theoretical Chemistry Mariapfarr – 12 / 64

 Symmetry of the Hamiltonian

Point Groups
Some Properties
Molecular Hamiltonian
Fundamental
approximations h̄2 X 2 X h̄2 2
H(R, r) = − ∇i + ∇ + V (R, r)
2MI I
Complete Nuclear
Permutation and 2me
Inversion (CNPI) i I
Groups

Rotational motion with the Coulomb interaction potential

Rigid Molecules
X ZI ZJ X 1 X ZI
Floppy Molecules
V (R, r) = + −
Non-rigid ~I − R
|R ~J| |~ri − ~rj | ~ I − ~ri |
|R
Molecules: Single I 6=J i6=j Ii
Potential Energy
Surface
Non-rigid
Invariances
Molecules:
Multiple Potential
Energy Surfaces
1. rotation,operator J 2
Summary and [H, J 2 ] = 0
Literature
2. permutation of any two identical particles, operator (12)
[H, (12)] = 0
3. inversion of the coordinate system, operator E ∗
[H, E ∗ ] = 0

Workshop on Theoretical Chemistry Mariapfarr – 13 / 64

Point Groups
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups
2 identical nuclei:
water
3 identical nuclei
Feasible
operations
Ammonia
Ethene
Linear molecules
Complete Nuclear Permutation and
Rotational motion Inversion (CNPI) Groups
Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 14 / 64

 CNPI group of water

Point Groups
Water: 2 identical H atoms, operators (12) and E ∗
Complete Nuclear
Permutation and
Inversion (CNPI) ■ Multiplication table of S2 × I permutation-inversion group:
Groups
2 identical nuclei:
water S2 × I E (12) E∗ (12)∗
3 identical nuclei
Feasible E E (12) E∗ (12)∗
operations
(12) (12) E (12)∗ E∗
Ammonia
Ethene E∗ E∗ (12)∗ E (12)
Linear molecules
(12)∗ (12)∗ E∗ (12) E
Rotational motion

Rigid Molecules ■ Multiplication table of C2v point group:

Floppy Molecules
Non-rigid C2v Ê Ĉ2 σ̂v σ̂v′
Molecules: Single
Potential Energy Ê Ê Ĉ2 σ̂v σ̂v′
Surface
Non-rigid
Ĉ2 Ĉ2 Ê σ̂v′ σ̂v
Molecules:
Multiple Potential
σ̂v σ̂v σ̂v′ Ê Ĉ2
Energy Surfaces
σ̂v′ σ̂v′ σ̂v Ĉ2 Ê
Summary and
Literature
■ The two groups are isomorphic.
■ Molecular symmetry group is called C2v (M).

Workshop on Theoretical Chemistry Mariapfarr – 15 / 64

 Permutation group of three identical particles

Point Groups
■ generated by operators (12) ≡ (21), (23) ≡ (32), (13) ≡ (31)
Complete Nuclear
Permutation and (12)[123] = [213] ; (23)[123] = [132] ; (13)[123] = [312]
Inversion (CNPI)
Groups ■ combinations yield cyclic permutations:
2 identical nuclei:
water (12)(23)[123] = (12)[132] = [231] ⇒ (123)[123]
3 identical nuclei
Feasible 1 replaced by 2, 2 replaced by 3, 3 replaced by 1
operations
Ammonia
Ethene
(23)(12)[123] = (23)[213] = [312] ⇒ (132)[123]
Linear molecules 1 replaced by 3, 3 replaced by 2, 2 replaced by 1
Rotational motion
■ Multiplication table:
Rigid Molecules

Floppy Molecules S3 E (12) (23) (13) (123) (132)

Non-rigid E E (12) (23) (13) (123) (132)
Molecules: Single
Potential Energy (12) (12) E (123) (132) (23) (13)
Surface
(23) (23) (132) E (123) (13) (12)
Non-rigid
Molecules: (13) (13) (123) (132) E (12) (23)
Multiple Potential
Energy Surfaces (123) (123) (13) (12) (23) (132) E
Summary and (132) (132) (23) (13) (12) E (123)
Literature

■ classes: E; {(12), (23), (13)}; {(123), (132)}

S3 isomorphic with C3v : (E, {3σv }, {2C3 )}

Workshop on Theoretical Chemistry Mariapfarr – 16 / 64

 CNPI group of three identical particles

Point Groups
CNPI group is S3 × I
Complete Nuclear
Permutation and
Inversion (CNPI) ■ operators: E, {(12), (23), (13)}, {(123), (132)}
Groups
2 identical nuclei:
and E ∗ , {(12)∗ , (23)∗ , (13)∗ }, {(123)∗ , (132)∗ }
water ■ S3 × I isomorphic with D3h
3 identical nuclei
Feasible ■ character table
operations
Ammonia S3 × I E {(123), (132)} {(12), (23), (13)} E∗ {(123)∗ , (132)∗ } {(12)∗ , (23)∗ , (13)∗ }
Ethene D3h E 2C3 3C2 σh 2S3 3σv
Linear molecules
A′1 1 1 1 1 1 1
Rotational motion A′2 1 1 -1 1 1 -1
Rigid Molecules E′ 2 -1 0 2 -1 0
A′′1 1 1 1 -1 -1 -1
Floppy Molecules
A′′2 1 1 -1 -1 -1 1
Non-rigid
Molecules: Single
E ′′ 2 -1 0 -2 1 0
Potential Energy
Surface ■ D3h (M) is the molecular symmetry group of H+
3 , BF3 , · · ·
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 17 / 64

 Longuet-Higgins: Not all operations are feasible

Point Groups
■ Two ”versions” of CH3 F. They differ from ordering (clockwise,
Complete Nuclear
Permutation and anti-clockwise) of H atoms looking along F ⇒ C
Inversion (CNPI)
Groups
2 identical nuclei:
water
3 identical nuclei
Feasible
operations
Ammonia
Ethene
Linear molecules

Rotational motion

Rigid Molecules ■ passing between the two structures only via high-energy planar
Floppy Molecules
transition state: not feasible
Non-rigid
Molecules: Single ■ hence (12), (23) and (13) are not feasible operations
Potential Energy
Surface ■ E ∗ not feasible either
Non-rigid
Molecules:
■ however (12)∗ etc. are feasible
Multiple Potential
Energy Surfaces
■ Molecular symmetry group C3v (M) by E, {(123), (132)}, {(12)∗ ,
Summary and (23)∗ , (13)∗ }
Literature
■ C3v (M) is a sub group of D3h (M) , see previous slide

Workshop on Theoretical Chemistry Mariapfarr – 18 / 64

 Ammonia NH3

Point Groups
■ CNPI group has order n = 1! × 3! × 2 = 12
Complete Nuclear
Permutation and ■ 2 versions of ammonia
Inversion (CNPI)
Groups
2 identical nuclei:
water
3 identical nuclei
Feasible
operations
Ammonia
Ethene ■ low inversion barrier: all operations feasible
Linear molecules

Rotational motion
■ Molecular symmetry group is D3h (M) = C3v (M) × (E , E ∗ ), order
Rigid Molecules
n = 12
Floppy Molecules ■ “doubling” of rovibrational states (symmetric and
Non-rigid
Molecules: Single
anti-symmetric with respect to (12) etc.), observable splitting
Potential Energy
Surface
Non-rigid
Molecules:
C3v (M) D3h (M)
Multiple Potential
Energy Surfaces
A1 A′1 + A′′2
Summary and A2 A′2 + A′′1
Literature
E E ′ + E ′′

Workshop on Theoretical Chemistry Mariapfarr – 19 / 64

 Ethene H2 C = CH2

Point Groups
■ CNPI group has order n = 2! × 4! × 2 = 96
Complete Nuclear
Permutation and ■ 12 versions of ethene
Inversion (CNPI)
Groups
2 identical nuclei:
water
3 identical nuclei
Feasible
operations
Ammonia
Ethene
Linear molecules

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface ■ unfeasible operations would rupture bonds, (12), (56) etc.
Non-rigid
Molecules:
■ feasible operations are E , (12)(34), (13)(24)(56), (14)(23)(56)
Multiple Potential
Energy Surfaces
and E ∗ , (12)(34)∗ , (13)(24)(56)∗ , (14)(23)(56)∗
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 20 / 64

 Ethene H2 C = CH2 : continued

Point Groups
■ feasible operations are E , (12)(34), (13)(24)(56), (14)(23)(56)
Complete Nuclear
Permutation and and E ∗ , (12)(34)∗ , (13)(24)(56)∗ , (14)(23)(56)∗
Inversion (CNPI)
Groups ■ 4 views of version (a): original plus result of three rotations
2 identical nuclei:
water (x, y , z)
3 identical nuclei
Feasible
operations
Ammonia
Ethene
Linear molecules

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
■ Molecular symmetry group is D2h (M), order
Molecules:
Multiple Potential
n = 8 = 96/number of versions, i.e. a subgroup of the CNPI
Energy Surfaces group
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 21 / 64

 Rigid linear molecules

Point Groups
■ OCS: E , E ∗ ; (C∞v (M))
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups
E E∗
2 identical nuclei:
water
Σ+ 1 1
3 identical nuclei Σ− 1 -1
Feasible
operations
Ammonia ■ H2 : E , (12), E ∗ , (12)∗ ; (D∞h (M))
Ethene
Linear molecules E (12) E ∗ (12)∗
Rotational motion
Σ+ g 1 1 1 1
Rigid Molecules

Floppy Molecules
Σ+ u 1 -1 1 -1
Non-rigid Σ− g 1 -1 -1 1
Molecules: Single
Potential Energy Σ− u 1 1 -1 -1
Surface
Non-rigid note that the point group operation i corresponds to (12)∗
Molecules:
Multiple Potential
Energy Surfaces ■ ethyne (acetylene), H(1) − C(3) ≡ C(4) − H(2) : as H2 but
Summary and
Literature
E , (12)(34), E ∗ , (12)(34)∗
■ extended molecular symmetry group (EMS) needed to classify
vibration (degenerate mode)

Workshop on Theoretical Chemistry Mariapfarr – 22 / 64

Point Groups
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion
Defintions
Rotating
molecules

Rigid Molecules

Floppy Molecules
Non-rigid
Rotational motion
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 23 / 64

 Rotational motion

Point Groups ■ Comparison of linear and angular motions

Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion
Defintions
Rotating
molecules

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
■ Angular momentum in molecule-fixed axis system (x ′ , y ′ , z ′ ):
Molecules:    P P ′ ′ P ′ ′  ′ 
Multiple Potential L′x ma (ya′ 2 + za′ 2 ) − xa ya − xa z a ωx
 L′y  P ′ ′ P P ′ ′
Energy Surfaces =  − y x ma (xa + za′ 2 )
′2
− ya z a   ωy′ 
P a′ a′ P ′ ′ P
Summary and L′z − z a xa − z a ya ma (ya′ 2 + za′ 2 ) ωz′
Literature

■ Principal axes by diagonalisation of tensor of inertia

L′ = I′ ω ′ = XX−1 I′ XX−1 ω ′ = XIX−1 ω ′

X−1 L′ = IX−1 ω ′
L = Iω

Workshop on Theoretical Chemistry Mariapfarr – 24 / 64

 Rotational motion: continued

Point Groups ■ Angular momentum in principal axis system (x, y , z):

Complete Nuclear    P  
Permutation and Lx ma (ya 2 + za 2 ) P 0 0 ωx
Inversion (CNPI)
Groups
 Ly  =  0 ma (xa 2 + za 2 ) P 0   ωy 
Lz 0 0 ma (ya 2 + za 2 ) ωz
Rotational motion
Defintions
Rotating ■ Rotational energy
molecules

Rigid Molecules
1 T 1 2 1 2 1 2
Floppy Molecules Erot = ω Iω = Ixx ωx + Iyy ωy + Izz ωz
2 2 2 2
Non-rigid 2
Molecules: Single L2x Ly L2z
Potential Energy = + +
Surface
2Ixx 2Iyy 2Izz
Non-rigid L2a L2b L2c
Molecules: = + +
Multiple Potential 2IA 2IB 2IC
Energy Surfaces 2 2 2
= ALa + BLb + CLc
Summary and
Literature

■ Spectroscopic convention for moments of inertia: IA ≤ IB ≤ IC

for rotational constants: A ≥ B ≥ C

Workshop on Theoretical Chemistry Mariapfarr – 25 / 64

 Rotational motion: continued

Point Groups 1. Linear polyatomic molecule: A = 0, B = C

Complete Nuclear
Permutation and Trot = AĴa2 + B(Ĵb2 + Ĵc2 ) = B(Ĵ 2 − Ĵa2 )
Inversion (CNPI)
2
Groups Erot = BJ(J + 1) − Bka
Rotational motion
2. Spherical top: A = B = C , example CH4
Defintions
Rotating
molecules Trot = B(Ĵa2 + Ĵb2 + Ĵc2 ) = B Ĵ 2
Rigid Molecules Erot = BJ(J + 1)
Floppy Molecules 3. Symmetric top: two rotational constants are equal
Non-rigid
Molecules: Single ■ prolate top: A > B = C , example CH3 F
Potential Energy
Surface 2 2 2 2 2 2 2 2
Trot = AĴa + B(Ĵb + Ĵc ) = B(Ĵ − Ĵa ) + AĴa = B Ĵ + (A − B)Ĵa
Non-rigid
Molecules: Erot = BJ(J + 1) + (A − B)ka2
Multiple Potential | {z }
Energy Surfaces > 0
Summary and
Literature Erot increases with Ka = |ka | for given J
■ oblate top: A = B > C , examples NH3 , BF3 , H+
3
2 2 2 2 2 2 2 2
Trot = B(Ĵa + Ĵb ) + C Ĵc = B(Ĵ − Ĵc ) + C Ĵc = B Ĵ + (C − B)Ĵc
Erot = BJ(J + 1) + (C − B)kc2
| {z }
< 0

Erot decreases with Kc = |kc | for given J

Workshop on Theoretical Chemistry Mariapfarr – 26 / 64

 Rotational motion: continued

Point Groups 4. Asymmetric top: A > B > C , example H2 O

Complete Nuclear
Permutation and Trot = AĴa2 + B(Ĵb2 + Ĵc2 )
Inversion (CNPI)
Groups 1 1
= AĴa2 + (B + C )(Ĵb2 + Ĵc2 ) + (B − C )(Ĵb2 − Ĵc2 )
Rotational motion 2 2
Defintions 2 1 2 2 1 +2 −2
Rotating = AĴa + (B + C )(Ĵ − Ĵa ) + (B − C )(Ĵ + Ĵ )
molecules 2 2
Rigid Molecules with Ĵ ± = Ĵb ± i Ĵc . Matrix elements in the prolate top |Jka i basis:
Floppy Molecules
′ 2 1 h
2
i
Non-rigid hJka |Trot |Jka i = Aka δka k ′ + (B + C ) J(J + 1) − ka δka k ′
Molecules: Single
a 2 a
Potential Energy 1 +2 ′ 1 −2 ′
Surface + hJka |Ĵ |Jka i + hJka |Ĵ |Jka i
2| {z } 2| {z }
Non-rigid
∼ δ ∼ δ
Molecules: ka ka′ +2 ka ka′ −2
Multiple Potential
Energy Surfaces
ka not conserved, but (−1)Ka is (likewise (−1)Kc ). Correlation with symmetric
Summary and tops:
Literature

Workshop on Theoretical Chemistry Mariapfarr – 27 / 64

 Rotational functions: Euler angles

Point Groups Representation of rotational functions and their symmetry

Complete Nuclear q
J∗
Permutation and ■ (θ, φ, χ|Jkmi = 2J+18π 2
Dmk (φ, θ, χ) ∼ e imφ dmk
J
(θ)e ikχ
Inversion (CNPI)
Groups J
Dkm are Wigner rotation functions, depending on the Euler angles θ, φ, χ
Rotational motion ■ molecule-fixed axes parallel to laboratory system: (ξ, η, ζ)
Defintions molecule-fixed axes equivalent to principal axes: (x, y , z)
Rotating k and m are internal,z, and exteral, ζ, projections
molecules

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

■ x, y , z axes defined with respect to numbered particles

■ permutation of particles then reorients (x, y , z) axes, hence the Euler angles
change
■ transformation of Euler angles in CNPI to be studied casewise: H2 , H2 O

Workshop on Theoretical Chemistry Mariapfarr – 28 / 64

 Rotational functions: linear molecule case

Point Groups ■ linear polyatomic molecules: A = 0, B = C

Complete Nuclear
Permutation and
Inversion (CNPI) Trot = AĴa2 + B(Ĵb2 + Ĵc2 ) = B(Ĵ 2 − Ĵa2 ) Erot = BJ(J + 1) − Bka2
Groups

Rotational motion ■ diatomic: Ja = ka = 0 since ~J ⊥ ~z , χ not defined

Defintions
Rotating
J∗
molecules Erot = BJ(J + 1) (θ, φ|Jmi ∼ Dm,k=0 (φ, θ, χ) ∼ YJm (θ, φ)
Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature
(E ∗ )(θ, φ) = (π − θ, φ + π) (12)(θ, φ) = (π − θ, φ + π) only for homonuclear

■ Effect on rotational function:

YJm (π − θ, φ + π) = (−1)J YJm (θ, φ)

Workshop on Theoretical Chemistry Mariapfarr – 29 / 64

Point Groups
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules
H2
Water
Summary

Floppy Molecules
Non-rigid
Rigid Molecules
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 30 / 64

 H2

Point Groups
■ Molecular symmetry group D∞h (M)
Complete Nuclear
Permutation and ■ Symmetry of vibrational function |v i:
Inversion (CNPI)
Groups R = |R ~1 − R
~ 2 |; invariant with respect to all symmetry operations
Rotational motion Γ(|v i) = Σ+g
Rigid Molecules ■ Symmetry of rotational function |Jmi: (m external projection)
H2
Water
Summary (12)(θ, φ, R) = (π − θ, φ + π, R)
Floppy Molecules (E ∗ )(θ, φ, R) = (π − θ, φ + π, R)
Non-rigid
Molecules: Single
Potential Energy
Surface
■ Effect on rotational function:
Non-rigid
Molecules: YJm (π − θ, φ + π) = (−1)J YJm (θ, φ)
Multiple Potential
Energy Surfaces ■ Character table:
Summary and
Literature D∞h (M) S2 × I E (12) E∗ (12)∗
Σ+
g A1 1 1 1 1 Ψ(R), YJm (J even)
Σ+
u B2 1 -1 1 -1
−
Σg B1 1 -1 -1 1 YJm (J odd)
Σ−
u A2 1 1 -1 -1

Workshop on Theoretical Chemistry Mariapfarr – 31 / 64

 H2 : continued

Point Groups
H2 isotopologues in the electronic ground state (X 1 Σ+ +
g ): Γel = Σg
Complete Nuclear
Permutation and |Ψi = |eli |nsi |vibi |roti
Inversion (CNPI)
Groups Γtot = Γel × Γns × Γvib × Γrot
Rotational motion
■ H2 : i = 1/2, i.e. fermion. |Ψi must be anti-symmetric (Σ+ −
u or Σg )
Rigid Molecules
H2  
Water 

 ↑↑

Summary triplet ↑↓ + ↓↑ I = 1, symmetric χ[(12)] = 1, Γ = A (Σ+ )
1 g
↑ + ↑= 

Floppy Molecules 
 ↓↓

singlet ↑↓ − ↓↑ I = 0, anti-symmetric χ[(12)] = −1, Γ = B2 (Σ+

Non-rigid u)
Molecules: Single
Potential Energy
Surface ■ Symmetry
Non-rigid
Molecules:
Multiple Potential
I = 1, J even : Γtot = Σ+ + + + +
g × Σg × Σg × Σg = Σg forbidden
Energy Surfaces
Summary and
I = 1, J odd : Γtot = Σ+ + + − −
g × Σg × Σg × Σg = Σg allowed
Literature
I = 0, J even : Γtot = Σ+ + + + +
g × Σu × Σg × Σg = Σu allowed

I = 0, J odd : Γtot = Σ+ + + − −
g × Σu × Σg × Σg = Σu forbidden

■ Missing levels (zero statistical weight):

J even for ortho-hydrogen (triplet), J odd for para-hydrogen (singlet)

Workshop on Theoretical Chemistry Mariapfarr – 32 / 64

 H2 : continued

Point Groups
■ D2 : i = 1, i.e. bosons. |Ψi must be symmetric (Σ+ −
g or Σu )
Complete Nuclear
Permutation and Nuclear spin functions: I = 2, 1, 0, symmetry Σ+ + +
g , Σu , Σg
Inversion (CNPI)
Groups
Γtot = Γel × Γns × Γvib × Γrot
Rotational motion

Rigid Molecules
I = 2, 0, J even : Γtot = Σ+ + + + +
g × Σg × Σg × Σg = Σg allowed
H2
Water
I = 2, 0, J odd : Γtot = Σ+ + + − −
g × Σg × Σg × Σg = Σg forbidden
Summary
I = 1, J even : Γtot = Σ+ + + + +
g × Σu × Σg × Σg = Σu forbidden
Floppy Molecules
Non-rigid
I = 1, J odd : Γtot = Σ+ + + − −
g × Σu × Σg × Σg = Σu allowed
Molecules: Single
Potential Energy
Surface
Non-rigid Missing levels (zero statistical weight):
Molecules:
Multiple Potential J even for I = 1, J odd for I = 2, 0
Energy Surfaces
■ HD: symmetry group C∞v (M) (no g /u classification)
Summary and
Literature
C∞v (M) I E E∗
Σ+ A1 1 1 Ψ(R), YJm (J even)
Σ− A2 1 -1 YJm (J odd)

all states are allowed

Workshop on Theoretical Chemistry Mariapfarr – 33 / 64

 Water

Point Groups ■ inversion

Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules
H2
Water E ∗ (θ, φ, χ) = (π − θ, φ + π, π − χ)
Summary

Floppy Molecules ■ permutation (equivalent x-rotation by π)

Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces (12)(θ, φ, χ) = (π − θ, φ + π, 2π − χ)
Summary and
Literature
it follows that (12)∗ (θ, φ, χ) = (θ, φ, χ + π), i.e. a z-rotation by π

■ effect on |Jkmi
(12)|Jkmi = (−1)J |J, −k, mi
∗ k
(12) |Jkmi = (−1) |J, k mi
E ∗ |Jkmi = (−1)J+k |J, −k, mi

Workshop on Theoretical Chemistry Mariapfarr – 34 / 64

 Water: continued

√1
Point Groups
■ Wang combinations: |J, K ±, mi = 2
(|J, k, mi ± |J, −k, mi)
Complete Nuclear
Permutation and ■ Transformation properties
Inversion (CNPI)
Groups

Rotational motion (12)|J, K +, mi = (−1)J |J, K +, mi

Rigid Molecules
(12)|J, K −, mi = (−1)J+1 |J, K −, mi
H2
Water (12)∗ |J, K ±, mi = (−1)K |J, K ±, mi
Summary

Floppy Molecules E ∗ |J, K +, mi = (−1)J+K |J, K +, mi

Non-rigid
Molecules: Single
E ∗ |J, K −, mi = (−1)J+K +1 |J, K −, mi
Potential Energy
Surface
Non-rigid
Molecules: ■ Symmetry (depends on group and axis convention)
Multiple Potential
Energy Surfaces
Summary and
|J, K ±, mi K χ[(12)] χ[E ∗ ] Γ
Literature J even J odd
|J, K +, mi even (−1)J (−1)J A1 B1
odd (−1)J (−1)J+1 A2 B2
|J, K −, mi even (−1)J+1 (−1)J+1 B1 A1
odd (−1)J+1 (−1)J B2 A2

Workshop on Theoretical Chemistry Mariapfarr – 35 / 64

 Water: rotational symmetry

Point Groups ■ The asymmetric top Hamiltonian is diagonalized in the Wang basis
Complete Nuclear ■ Degenerate symmetric top states are split into two parity components
Permutation and ■ Prolate (Ka ) and oblate (Kc ) quantum numbers used for labelling
Inversion (CNPI)
Groups ■ Symmetry of rotational functions |JKa Kc i:
Rotational motion

Rigid Molecules
H2
Water
Summary

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

■ symmetric w.r.t. (12):

A1 , A2 , to be combined with singlet nuclear spin of protons (para)
anti-symmetric w.r.t. (12):
B1 , B2 , to be combined with triplet nuclear spin of protons (ortho)
(just as in H2 )

Workshop on Theoretical Chemistry Mariapfarr – 36 / 64

 Water: vibrational symmetry

Point Groups
Symmetry of vibrational functions |v1 v2 v3 i:
Complete Nuclear
Permutation and
Inversion (CNPI) ■ Γ(ν1 ) = A1 , Γ(ν2 ) = A1 , Γ(ν3 ) = B2
Groups

Rotational motion
■ Examples:
Rigid Molecules Γ(|200i) = A1 × A1 = A1 ,
H2
Water
Γ(|002i) = B2 × B2 = A1 ,
Summary Γ(|011i) = A1 × B2 = B2 ,
Floppy Molecules
Γ(|111i) = A1 × A1 × B2 = B2 , etc.
Non-rigid
Molecules: Single
Potential Energy ■ Rules for direct products:
Surface
Non-rigid A × A = A, A × B = B, B × A = B, B × B = A,
Molecules:
Multiple Potential “1” × “1” = “1”, “1” × “2” = “2”, “2” × “1” = “2”, “2” × “2” = “1”
Energy Surfaces
Summary and
■ General expression:
Literature (
A1 if v3 even
Γ(|v1 v2 v3 i) = Av11 × Av12 × B2v3 =
B2 if v3 odd

Workshop on Theoretical Chemistry Mariapfarr – 37 / 64

 Water: rovibrational symmetry

Point Groups
■ Symmetry: Γrovib = Γrot × Γvib
Complete Nuclear
Permutation and
Inversion (CNPI) Ka Kc Γ(weight)
Groups
v3 even v3 odd
Rotational motion
e e A1 (1) B2 (3)
Rigid Molecules
H2 e o B1 (3) A2 (1)
Water
Summary
o e B2 (3) A1 (1)
Floppy Molecules
o o A2 (1) B1 (3)
Non-rigid
Molecules: Single Note: A symmetry states to be combined with singlet nuclear spin B2 ,
Potential Energy
Surface B symmetry states to be combined with triplet nuclear spin A1
Non-rigid ■ µ) = A2 (antisymm. w.r.t. E ∗ )
Dipole transition rules: Γ(~
Molecules:
Multiple Potential
Energy Surfaces Γ(hΨi |~
µ|Ψf i) = A1
Summary and
Literature ↽ A2 , B 1 ⇀
Possible transitions: A1 ⇀ ↽ B2 with ∆J = 0, ±1

Workshop on Theoretical Chemistry Mariapfarr – 38 / 64

 Summary for rigid molecules

Point Groups
Comments:
Complete Nuclear
Permutation and
Inversion (CNPI) 1. disadvantage of CNPI group: may be very large
Groups
2. use subgroup built up by feasible operations: equivalent to
Rotational motion

Rigid Molecules
point group for rigid molecules
H2 3. exact quantum numbers are J, Γ, n (n is a counting index)
Water
Summary 4. spectroscopic (vib, rot) quantum numbers are not exact, but
Floppy Molecules often “good”quantum numbers
Non-rigid
Molecules: Single
5. “spectroscopic” states with same exact symmetry may interact
Potential Energy
Surface
and lead to perturbations in the spectra
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 39 / 64

Point Groups
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Singlet H+
3
Non-rigid
Molecules: Single
Potential Energy
Floppy Molecules
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 40 / 64

 H+
3 : orbitals and electronic states

Point Groups
config. states

21
Complete Nuclear
Permutation and
D3h others
2
a1′ X 1 A′1

H
Inversion (CNPI)
Groups
g+ a1′ e ′ a 3E ′ → a 3 Σ+ 3 ′
u & 2 A

H
Rotational motion
A 1E ′ → A 1 Σ+ & 3 1 A ′
Rigid Molecules
2

Floppy Molecules

2
18

18
e

H
0

Singlet H+
3
Non-rigid
H

H
Molecules: Single
Potential Energy
Surface u+

H
Non-rigid 19

Molecules:
Multiple Potential
2

17
2

Energy Surfaces
H

Summary and
Literature

1
H

a1 0
g+
H

1
H

D3h D
1 h

Resulting ele troni states

Workshop on Theoretical Chemistry ong state Mariapfarr – 41 / 64

a12
0
X 1 A1
0
 
 H+
3 : vibrational symmetry

Point Groups
■ Normal modes: ν1 , ν2|ℓ| , ℓ = −v2 , −v2 + 2, · · · v2 (vibrational angular momentum)
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Singlet H+
3
Non-rigid
Molecules: Single
Potential Energy
Surface ■ Symmetry classification in S3 × I ≡ D3h (M): Γ(ν1 ) = A′1 , Γ(ν2 ) = E ′
Non-rigid ■ v2 = 1 → v2|ℓ| = 11 (E ′ ), ℓ = ±1
Molecules:
Multiple Potential ■ Overtones of ν2 : (only symmetric products)
Energy Surfaces
Summary and v2 = 2: Γ = E ′ × E ′ = A′1 + [A′2 ] + E ′
Literature
A′1 : 21 {(v2x v2y ) + (v2y v2x )} = v2x v2y
A′2 : 12 {(v2x v2y ) − (v2y v2x )} = 0
E ′ : {(v2x )2 , (v2y )2 }
|ℓ| |ℓ|
v2 = 2 → v2 = 22 (E ′ ), |v2 = 20 (A′ )
|ℓ| |ℓ|
v2 = 3 → v2 = 33 (A′1 + A′2 ), v2 = 31 (E ′ )

Workshop on Theoretical Chemistry Mariapfarr – 42 / 64

 H+
3 : rotational symmetry

Point Groups
■ H+
3 is an oblate symmetric top
Complete Nuclear |ℓ|
Permutation and
|vib, roti = |v1 , v2 i|JKc i
Inversion (CNPI) ■ nuclear spin: 3 protons (i = 1/2): quartet (I = 3/2, A′1 ), doublet (I = 1/2, E ′ )
Groups
■ vibrational state (0, 00 ): low J allowed rotational states
Rotational motion

Rigid Molecules J Kc Γrovib Γtot

Floppy Molecules
I = 3/2 I = 1/2
Singlet H+
0 0 A′1 - -
′′
3
1 1 E - A2 + (A′′
′′
1 +E )
′′
Non-rigid 0 A′2 A′2 -
Molecules: Single
Potential Energy 2 2 E′ - ′
A2 + (· · · )
Surface 1 E ′′ - A′′
2 + (· · · )
Non-rigid 0 A′1 - -
Molecules: 3 3 A′1 + A′2 ′
A2 , − -
Multiple Potential
Energy Surfaces 2 E′ - ′
A2 + (· · · )
Summary and
1 E ′′ - A′′
2 + (· · · )
Literature 0 A′2 A′2 -

■ vibrational state (0, 11 ): more complicated, ℓ (vibrational angular momentum) to

be coupled with molecular rotation
see, for example, Mol. Phys. 101, 175 (2003)

Workshop on Theoretical Chemistry Mariapfarr – 43 / 64

 floppy H+
3 : large amplitude motion

Point Groups from J. Gottfried, Oka group (Chicago): J. Chem. Phys. 118, 10890 (2003)
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Singlet H+
3
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

■ so far we have classified spectroscopic quantum numbers (v1 , v2|ℓ| ) in exact

symmetry group
■ “spectroscopic” states with same symmetry may “perturb” each other
■ above “barrier to linearity” spectroscopic quantum numbers begin to fail
■ J and exact CNPI quantum numbers hold: J, Γ, n, with n a counting index
■ compute rovibrational states using coordinates not derived from potential
minimum: hyperspherical coordinates

Workshop on Theoretical Chemistry Mariapfarr – 44 / 64

   X
3 r
mk mk mi mj mk
dk = 1 ; MN = mn ; = (2)
 + MN n =1
MN
floppy
The ranges of theH : coordinate
oordinates are: systems
3 permutation of the three parti le
Here, (i; j; k) is a y li
for triatomics
indi es. Apart from
  < 1; s aling
the mass 0dependent 0 =2;
parameter 0 d ,rk k<is4the internu lear distan e
k
(4) between
parti les i and
The three dierent Rk onne ts
j andarrangement theirreferred
hannels enter to of inmass to the third
the denition of theparti le
Ja- k as
obi ve tors an be
illustrated in gure 1.k identied by one unique angle in terms of hyperspheri al
Point Groups ■ oordinates:
JacobiOnly  depends on the initially hosen Ja obi system.
coordinates: rk , Rk
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion k=1 k=2 k=3

dk rk and dk 1 Rk for the three Ja obi systems.
Rigid Molecules
FigureHyperspherical
■ 1: The Ja obi ve tors
coordinates:
Floppy Molecules
internal coordinates: ρ, θ, φ , Euler angles: φE , θ E , χE
Singlet H+ 1 = 12 
3
Non-rigid
The External (Orientation) Coordinates are the three Euler angles (; ; )
Molecules: Single that spe ify the orientation of the mole ule with respe t to the spa e xed o-
Potential Energy ordinate system. The body xed z-axis (zkA, A = 21 rk  Rk ) is by denition
Surface perpendi ular to the plane formed by the three parti les and independent of the
Non-rigid arrangement index k. The third Euler angle is hosen as to orient the body
Molecules: xed-x and y axes along the other two prin ipal moments of inertia.
Multiple Potential
Energy Surfaces
The Internal
1 = 
(Conguration) Coordinates onsist of the1 hyperradius
=0

Summary and that determines the overall size of the triangle and the two hyperspheri al angles
Literature
 and 
q
2
 = jrj2 + jRj2 os  =  2
jAj os k = (rk
Rk ) (3)
2 sin 
that determine the shape.

1 = 32 2

Hyperpsherical harmonics, Ψ(θ, φ, φE , θ E , χE ) may be symmetrized within S3 × I

■Figure 2: Congurations of three identi al nu lei dened by the internal hyper-
and oordinates
spheri al allow exact A) and 0  1 < 2 . The pi tograms
(; ; 1 ) computations
( = 1:2 
approximately oin ide with the orresponding values of 1 and  whi h dene
the stru ture.
Workshop on Theoretical Chemistry 3 Mariapfarr – 45 / 64
Point Groups
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Non-rigid Molecules: Single Potential
Surface
Ammonia
Water dimer
Energy Surface
Triplet H+
3
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 46 / 64

 Non-rigid Ammonia

Point Groups ■ 3N − 6 = 6 vibrational modes: in the C3v point group Γvib = 2A1 + 2E
Complete Nuclear two versions, tunneling feasible: full CNPI group S3 × I , molecular symmetry
Permutation and group D3h (M)
Inversion (CNPI)
Groups

Rotational motion
mode C3v (M) mode D3h (M)
designation Γ designation Γ
Rigid Molecules
ν1 symmetric stretch A1 A′1
Floppy Molecules ν2 bending A1 νinv inversion A′′
2
Non-rigid ν3 E E′
Molecules: Single ν4 E E′
Potential Energy
Surface
Ammonia
■ character table
Water dimer S3 × I E {(123), (132)} {(12), (23), (13)} E∗ {(123)∗ , (132)∗ } {(12)∗ , (23)∗ , (13)∗ }
Triplet H+ D3h (M) C3v (M) E 2C3 3C2 σh 2S3 3σv
3
A′1 A1 1 1 1 1 1 1
Non-rigid A′2 A2 1 1 -1 1 1 -1
Molecules: E′ E 2 -1 0 2 -1 0
Multiple Potential A′′ 1 1 1 -1 -1 -1
1
Energy Surfaces
A′′
2 1 1 -1 -1 -1 1
Summary and E ′′ 2 -1 0 -2 1 0
Literature

Workshop on Theoretical Chemistry Mariapfarr – 47 / 64

 Non-rigid Ammonia: continued

Point Groups
■ bending levels v2 split into v2± ≡ vinv
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion
v2± vinv
Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Ammonia
Water dimer
′ ′
Triplet H+
3
■ nuclear spin functions as in H+
3 : I = 3/2 (Γ = A1 ), I = 1/2 (Γ = E )
Non-rigid Γns Γrovib Γtot
Molecules: A′1 A′2 A′1 × A′2 = A′2
Multiple Potential
Energy Surfaces A′′
2 A′1 × A′′
2 = A2
′′

Summary and
E′ E′ E ′ × E ′ = A′2 (+A′1 + E ′ )
Literature E ′′ E ′ × E ′′ = A′′ ′′
2 (+A1 + E )
′′

2n
■ missing levels: vinv , Γ = (A′′ ′′ n ′
2 × A2 ) = A1
■ also missing: overtones with A′1 symmetry, for example |v1 , v2 , v3 , v4 i = |0, 0, 2, 0i
Γ(|0, 0, 2, 0i) = A1 × A1 × E 2 × A1 = A1 + E → (A′1 + A′′ ′ ′′
2 ) + (E + E )
■ reverse correlation table with proton statistical weights
C3v (M) A1 (4) A2 (4) E (4)
′ ′′ ′ ′′
D3h (M) A1 (0) + A2 (4) A2 (4) + A1 (0) E (2) + E ′′ (2)
′

Workshop on Theoretical Chemistry Mariapfarr – 48 / 64

 Water dimer

Point Groups ■ Order of CNPI group = 4! × 2! × 2 = 96, order of the Cs point group of rigid
Complete Nuclear dimer = 2, hence 96/2 = 48 versions
Permutation and ■ Donor-acceptor complex: H2 O · · · HOH
Inversion (CNPI) |{z} | {z }
Groups donor
acceptor
Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface ■ feasible operations:
Ammonia
Water dimer 1. exchange of acceptor H atoms by rotation, “acceptor switching”,
Triplet H+ ∆E ≈ 200cm−1
3
2. exchange of donor H atom that makes hydrogen bond, “bifurcation”,
Non-rigid
Molecules:
∆E ≈ 650cm−1
Multiple Potential 3. exchange of donor and acceptor roles, “donor-acceptor interchange”,
Energy Surfaces ∆E ≈ 300cm−1
Summary and
Literature hence 2 × 2 × 2 = 8 connected versions
■ 6 sets of 8 versions, passing between sets involves bond breaking. Not feasible

Workshop on Theoretical Chemistry Mariapfarr – 49 / 64

 Water dimer: continued

Point Groups H2 O · · · HOH

|{z} | {z }
Complete Nuclear
acceptor donor
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Ammonia
Water dimer
Triplet H+
3
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

■ acceptor switching: for example (1) ⇀↽ (4)

■ donor-acceptor interchange: for example (1) ⇀↽ (5)
■ bifurcation (donor tunnelling): for example (1) ⇀
↽ (2)

Workshop on Theoretical Chemistry Mariapfarr – 50 / 64

 Water dimer: continued

Point Groups each hypothetical rigid dimer state is split into eight states, observable
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Ammonia
Water dimer
Triplet H+
3
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature

1. acceptor switching, ∆E ≈ 200cm−1

2. donor-acceptor interchange, ∆E ≈ 300cm−1
3. bifurcation (donor switching), ∆E ≈ 650cm−1
can be surpassed by donor-acceptor interchanges (1) ⇀
↽ (5) ⇀
↽ (2)

Workshop on Theoretical Chemistry Mariapfarr – 51 / 64

 Triplet H+
3 : delocalized ro-vibrational states

Point Groups
H+
3 : Phys. Rev. Lett. 86, 1183 (2001) ; J. Mol. Spectrosc. 221, 163 (2003)
Complete Nuclear
Permutation and
H2 D+ : J. Phys. Chem. A 110, 110 (2006)
Inversion (CNPI) D+
3 : J. Chem Phys. 128, 054301 (2008)
Groups

Rotational motion −1.0900

−1.0925 2−3−1
−1.0950 8
Rigid Molecules −1.0975
−1.1000 6
Floppy Molecules −1.1025 1−(3,2) (1,3)−2
−1.1050 4
Non-rigid −1.1075
−1.1100 2
Molecules: Single −1.1125
Potential Energy −1.1150 0 y
Surface −2
Ammonia 3 3 −4
− −

− −
Water dimer 2 1 −6
Triplet H+ 1 2
3 (1,2)−−3 −8

Non-rigid −8 −6 −4 −2 0 2 4 6 8
Molecules: x
Multiple Potential
Energy Surfaces
Summary and
|Ψ±
Ai ∼ |Ψ±
I i+ |Ψ±
II i + |Ψ±
III i
Literature
|Ψ±
E ,ξ i ∼ |Ψ± ± 2 ±
I i + ω |ΨII i + ω |ΨIII i
2πi
|Ψ±
E ,η i ∼ |Ψ± 2 ± ±
I i + ω |ΨII i + ω |ΨIII i ; ω=e 3

1 |ℓ|
|Ψ± i = √ |v1 v2 v3 i (|Nℓi ± |N − ℓi)
2

Workshop on Theoretical Chemistry Mariapfarr – 52 / 64

 Symmetry of localized ro-vibrational states

Point Groups ■ linear molecule, D∞h (M)

Complete Nuclear ■ normal modes:
Permutation and ν1 (symmetric stretch), ν2 (bending), ν3 (anti-symmetric stretch)
Inversion (CNPI)
Groups ■ symmetry classification in S3 × I and D∞h (M):
Γ(ν1 ) = A′1 , (Σ+ ′
g ), Γ(ν2 ) = E , (Πu ), (does not exist purely vibrational),
Rotational motion
Γ(ν3 ) = A′2 , (Σ+ u)
Rigid Molecules
vibrational angular momentum of ν2 : ℓ = −v2 , −v2 + 2, · · · v2
Floppy Molecules ■ rovibrational states:
|ℓ|
Non-rigid Ψ± = |v1 , v2 , v3 i √12 (|N, ℓ, mi ± |N, −ℓ, mi)
Molecules: Single
Potential Energy N = J − S, ℓ is its a-axis projection
Surface ■ electronic symmetry: Σ+ u
Ammonia ■ rovibronic symmetry of rigid triplet H+ 3
Water dimer
Triplet H+
3 mode Γvib Γrovib Γrovibr = Γrovib × Γel
Non-rigid S3 × I D∞h N even N odd N even N odd
Molecules: ′
Multiple Potential (1, 0, 0) A1 Σ+
g
+
Σg Σ−
g Σu +
Σ−u
Energy Surfaces (0, 11 , 0)+ E′ “Πu ” Σ−u Σ +
u Σ− g Σ +
g
− −
Summary and (0, 11 , 0)− +
Σu Σu Σg Σg+
Literature
(0, 0, 1 A′2 Σ+
u
+
Σu Σ−
u Σg −
Σ+g

Workshop on Theoretical Chemistry Mariapfarr – 53 / 64

 Symmetry of delocalized ro-vibrational states

Point Groups
■ Tunnelling triplet H+
3 : all CNPI, S3 × I , operations feasible,
Complete Nuclear molecular symmetry group is D3h (M)
Permutation and
Inversion (CNPI)
■ Reverse correlation table
Groups
D∞h (M) D3h (M) D∞h (M) D3h (M)
Rotational motion
Σ+
g (2) A′1 (0) + E ′ (2) Σ+
u (6) A′2 (4) + E ′ (2)
Rigid Molecules
Σ−
g (6) A′′ ′′
2 (4) + E (2) Σ−
u (2) A′′ ′′
1 (0) + E (2)
Floppy Molecules
Non-rigid ■ Nuclear spin effect:
Molecules: Single
Potential Energy
quartet I = 3/2, A′1 , combines with A′2 and A′′
2 rovibronic symmetry
Surface doublet I = 1/2, E , combines with E and E ′′ rovibronic symmetry
′ ′

Ammonia ■ Rovibronic symmetry of tunneling triplet H+ 3

Water dimer
Triplet H+ state Γrovib Γrovibr = Γrovib × A′2
3
Non-rigid N even N odd N even N odd
Molecules: (1, 0, 0) A′1 + E ′ A′′
2 + E ′′ ′
A2 + E ′
A′′1 +E
′′
Multiple Potential
Energy Surfaces (0, 11 , 0)+ A′′
1 +E
′′
A′2 + E′ A′′
2 +E
′′
A′1 + E ′
Summary and
(0, 11 , 0)− A′2 + E ′ A′′
1 + E ′′ A′1 + E ′ A′′2 +E
′′

Literature (0, 0, 1) A′2 + E ′ A′′

1 + E ′′ A′1 + E ′ A′′2 +E
′′

Workshop on Theoretical Chemistry Mariapfarr – 54 / 64

Point Groups
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Non-rigid Molecules: Multiple Potential
Surface
Non-rigid Energy Surfaces
Molecules:
Multiple Potential
Energy Surfaces
Triplet H+ ,
3
Jahn-Teller effect
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 55 / 64

 Lowest triplet states of H+
3 : view of surfaces

Point Groups
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Triplet H+ ,
3
Jahn-Teller effect
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 56 / 64

 H+
3 : Characterisation of the 3 ′
E surface

Point Groups
■ upper sheet:
Complete Nuclear
Permutation and dissociation channel: 2H (2 S) + H+ , −1.0000 Eh
Inversion (CNPI)
Groups energy minimum: (D3h ): −1.034590 Eh , r = 3.610 a0
Rotational motion ■ lower sheet:
Rigid Molecules
dissociation channel: H+ 2 + 2
2 ( Σg ) + H ( S), −1.102634 Eh
Floppy Molecules
Non-rigid
energy minimum: (D∞h ): −1.116106 Eh , r = 2.454 a0
Molecules: Single
Potential Energy
Surface
−1.0900 depth: 2947 cm−1
−1.0925 2−3−1
Non-rigid
−1.0950
−1.0975
8
barrier height: 2598 cm−1
Molecules: −1.1000 6
Multiple Potential −1.1025 1−(3,2) (1,3)−2
Energy Surfaces −1.1050 4
Triplet H+ ,
−1.1075
−1.1100 2
van der Waals complex
3
Jahn-Teller effect −1.1125
−1.1150 0 y H
Summary and
Literature −2 H · · · · · · |⊕
3 3 −4 H
− −

2 − −
1 −6
1 2
(1,2)−−3 −8

−8 −6 −4 −2 0 2 4 6 8
x

Workshop on Theoretical Chemistry Mariapfarr – 57 / 64

 Geometrical phase

Point Groups Longuet-Higgins, Adv. Spectrosc. 2, 429 (1961)

Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Triplet H+ ,
3
Jahn-Teller effect
Summary and ■ adiabatic electronic wave functions ϕ:
Literature

I2π
dφ ϕ(Q1 , Q2 , φ; r) = π
0

■ boundary conditions for rovibrational wave functions Θ:

Ψ(Q1 , Q2 , φ = 0) = −Ψ(Q1 , Q2 , φ = 2π)

Workshop on Theoretical Chemistry Mariapfarr – 58 / 64

 Triplet H+
3 : Including geometrical phase

Point Groups A. Alijah, V. Kokoouline, Chem. Phys. 460, 43 (2015)

Complete Nuclear
Permutation and Lowest vibrational A′1 state in diabatic representation, upper and lower components
Inversion (CNPI) Plot in hyperspherical coordinates
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Triplet H+ ,
3
Jahn-Teller effect
Summary and
Literature

Workshop on Theoretical Chemistry Mariapfarr – 59 / 64

 1-state (adiabatic) and 2-state (diabatic)
calculations
Point Groups
Complete Nuclear
Permutation and
1-state calculation 2-state calculation
Inversion (CNPI)
Groups (v1 , v2ℓ , v3 ) i A′1 i A′2 i E′
i A′1 i A′2 i E′
0
Rotational motion (0, 0 , 0) 0 0.00 0 0.00 0 0.00 0 1.04
(0, 00 , 1) 0 738.49 1 738.49 0 738.91 1 738.86
Rigid Molecules
(1, 00 , 0) 1 975.05 2 975.07 1 975.34 2 976.08
Floppy Molecules (0, 20 , 0) 2 1273.73 3 1273.80 2 1274.13 3 1274.98
Non-rigid (1, 00 , 1) 1 1474.51 4 1474.49 1 1475.24 4 1475.19
Molecules: Single (0, 00 , 2) 3 1573.69 5 1573.87 3 1574.17 5 1574.92
Potential Energy
Surface (0, 20 , 1) 2 1730.35 6 1728.45 2 1730.77 6 1728.84
Non-rigid
(2, 00 , 0) 4 1922.54 7 1923.12 4 1922.94 7 1923.80
Molecules: (1, 20 , 0) 5 1940.32 3 8 1951.07 5 1940.88 3 8 1951.76
Multiple Potential (0, 00 , 3) 4 1972.74 9 1970.85 4 1974.17 9 1972.24
Energy Surfaces
(1, 00 , 2) 6 2158.70 10 2137.06 6 2159.79 10 2137.86
Triplet H+ ,
3 (0, 40 , 0) 7 2188.46 11 2166.46 7 2189.69 11 2167.77
Jahn-Teller effect
(2, 00 , 1) 5 2204.86 12 2251.08 5 2205.80 12 2253.44
Summary and
Literature
(1, 20 , 1) 6 2271.04 13 2259.41 6 2273.62 13 2261.07
(0, 20 , 2) 8 2308.68 14 2308.76 8 2311.55 14 2338.04
(3, 00 , 0) 9 2340.10 15 2335.12 9 2341.46 15 2358.48
7 2402.71 7 2407.11 16 2363.82
10 2374.13 7 16 2363.82
11 2403.16 17 2396.43
12 2407.11 18 2413.19
13 2423.89 19 2417.62
20 2429.16

Workshop on Theoretical Chemistry Mariapfarr – 60 / 64

 Symmetry properties in diabatic and diabatic
picture

′
Point Groups
1. adiabatic (one-state) representation: electronic state 3 Σ+
u , symmetry A2 in CNPI
Complete Nuclear symmetry of vibrational states
Permutation and
Inversion (CNPI) ■ ortho nuclear spin
Groups
Γel × Γns = A′2 × A′1 = A′2 , vibrational state must have A′1 symmetry
Rotational motion Γtot = Γel × Γns × Γvib = A′2 × A′1 × A′1 = A′2
Rigid Molecules ■ para nuclear spin
Floppy Molecules
Γel × Γns = A′2 × E ′ = E ′ , vibrational state must have E ′ symmetry
Γtot = Γel × Γns × Γvib = A′2 × E ′ × E ′ = A′2 (+A′1 + E ′ )
Non-rigid
Molecules: Single
Potential Energy 2. diabatic (two-state) representation: electronic state 3 E ′ , symmetry E ′ in CNPI
Surface symmetry of vibrational states
Non-rigid
Molecules: ■ ortho nuclear spin
Multiple Potential Γel × Γns = E ′ × A′1 = E ′ , vibrational state must have E ′ symmetry
Energy Surfaces Γtot = Γel × Γns × Γvib = E ′ × A′1 × E ′ = A′2 (+A′1 + E ′ )
Triplet H+ , ■ para nuclear spin
3
Jahn-Teller effect Γel × Γns = E ′ × E ′ = A′1 + A′2 + E ′ , vibrational state may have

any symmetry
Summary and ′ ′ ′ ′ ′ ′
Literature
 E × E × A1 = A2 +A1 + E

′ ′ ′
Γtot = Γel × Γns × Γvib = E × E × A2 = A′2 +A′1 + E ′

 ′
E × E′ × E′ = A′2 +A′1 + 3E ′
3. statistical weights of vibrational states
Γvib W (1 st.) W (2 st.)
′
A1 4 2
′
A2 0 2 may be helpful to detect geometrical phase
′
E 2 6

Workshop on Theoretical Chemistry Mariapfarr – 61 / 64

Point Groups
Complete Nuclear
Permutation and
Inversion (CNPI)
Groups

Rotational motion

Rigid Molecules

Floppy Molecules
Non-rigid
Molecules: Single
Potential Energy
Surface
Summary and Literature
Non-rigid
Molecules:
Multiple Potential
Energy Surfaces
Summary and
Literature
Summary
Literature

Workshop on Theoretical Chemistry Mariapfarr – 62 / 64

 Summary

Point Groups ■ Point group symmetry is approximate and can only be used for rigid molecules
Complete Nuclear ■ The CNPI, complete nuclear permutation inversion group, introduced by
Permutation and Longuet-Higgins, gives the exact symmetry
Inversion (CNPI)
Groups ■ CNPI may be very large, unfeasible operations are removed to obtain the
molecular symmetry (MS) group.
Rotational motion
Example: ethene, order of CNPI group = 2! × 4! × 2 = 96. The MS group (D2h (M)
Rigid Molecules has order 8.
Floppy Molecules ■ CNPI describes rigid molecules, in this case the CNPI group is isomorphic with
Non-rigid the point group.
Molecules: Single Example: water, order of CNPI group = 2! × 1 × 2 = 4, order of point group C2v
Potential Energy is 4. The MS group is C2v (M).
Surface
■ CNPI describes floppy molecules that strongly depart from equilibrum
Non-rigid
Molecules:
configuration.
Multiple Potential Example: singlet H+3 , triangle at equilibrium, but linear configurations accessible
Energy Surfaces at high energy. Breakdown of point group classification of vibrational states.
Summary and ■ CNPI describes non-rigid molecules that have more than one minimum on the
Literature potential energy surface.
Summary Example: ammonia, weakly bound complexes such as the water dimer
Literature
■ CNPI describes non-rigid molecules that cannot be treated within the adiabatic
approximation of a single electronic state. The participating electronic states
may have different symmetry.
Example: triplet H+3 which shows a Jahn-Teller effect

Workshop on Theoretical Chemistry Mariapfarr – 63 / 64

 Literature

Point Groups 1. H. C. Longuet-Higgins, The Symmetry Groups of Non-rigid Molecules,

Complete Nuclear Mol. Phys. 6, 445-460 (1963)
Permutation and 2. J. T. Hougen, Classification of Rotational Energy Levels for SymmetricTop
Inversion (CNPI)
Groups Molecules,
J. Chem. Phys. 37, 1433-1441 (1962)
Rotational motion
3. J. T. Hougen, Classification of Rotational Energy Levels. II, J. Chem. Phys. 39,
Rigid Molecules 358-365
Floppy Molecules (1963)
Non-rigid
4. D. Papoušek & M. R. Aliev, Molecular Vibrational and Rotational Spectra,
Molecules: Single Elsevier, Amsterdam (1982)
Potential Energy out of print
Surface
5. P. R. Bunker & P. Jensen, Molecular Symmetry and Spectroscopy, NRC
Non-rigid Research Press, Ottawa (2006)
Molecules:
Multiple Potential printed on demand
Energy Surfaces 6. P. R. Bunker & P. Jensen, Fundamentals of Molecular Symmetry, Institue of
Summary and Physics, Bristol (2005)
Literature (kind of concise version of the above)
Summary 7. P. Bernath, Spectra of Atoms and Molecules, Oxford University Press (2016),
Literature third edition
(excellent general reference on high resolution spectroscopy, but not CNPI)

Illustrations used in this presentation are taken from the above references

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