Effects of Displacement–Distortion of Potential Energy Surfaces on Nonadiabatic Electron Transfers via Conical Intersections: Application to SO<sub>2</sub> and <i>trans</i>-1,3,5-Hexatriene

Zeidabadinejad, Leila; Dehestani, Maryam

doi:10.1021/acs.jpca.6b01849

Cited by 3 publications

(8 citation statements)

References 67 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The diabatic PESs often have simple structures and can be well approximated using the harmonic potentials [26]. So, to eliminate the linear vibronic expressions, we use the Duschinsky transformation [24] which can be related to each other the normal coordinates of excited electronic states to the normal coordinate of ground electronic state (Equation ).

Ω^{'' - bold1 / bold2} {bold-italicQ}^{'}^{(n)} = bold-italicJ Ω^{'' - bold1 / bold2} Q^{''} + D^{(bold-italicn)} n = ((), a, d)

where Ω ″ is a diagonal matrix of the vibrational frequencies of ground electronic state

({}, ω_{j}^{''})

, J is the Duschinsky rotation matrix and D ( n ) is a N ‐dimensional column vector which are the ith mode nuclear equilibrium positions displacement of the excited electronic state n with respect to those of ground electronic state (

d_{i}^{(n)}

) and is nonzero for the totally symmetric modes.…”

Section: Computational Details and Theoretical Considerationsmentioning

confidence: 99%

“…For investigation of non‐adiabatic electronic population dynamics we used a general expression for electronic population at any time on systems involving a CI using time correlation function formalism for two vibronically coupled diabatic displaced‐distorted harmonic PESs that obtained from our previous work [26]. For evaluating vibronic coupling and non‐adiabatic population dynamics we need to correctly determine the equilibrium geometry and harmonic vibrational frequencies on the ground electronic state, first and second excited states of F 2 O + cation.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Investigation of nonadiabatic coupling and diabatic electronic population dynamics on F₂O⁺ cation within multi reference configuration interaction calculations

Dehestani

2021

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

In F2O+ cation the first (2B2) and second excited (2A1) electronic states can be coupled with each other by anti‐symmetric stretching mode and thus conical intersection and non‐adiabatic dynamics play an important role in characterizing molecular properties. In this work, we tried to find a suitable computational method for determining equilibrium structures and harmonic vibrational frequencies of the three lowest electronic states of F2O+. To understand non‐adiabatic dynamics at conical intersections, we calculated the probability of electronic population on 2B2 and 2A1 excited electronic states using linear vibronic coupling Hamiltonian mode including all three vibrational modes (bending (ω1), symmetric stretching (ω2) and anti‐symmetric stretching (ω3)).The amount of vibronic coupling constant between these states is obtained 0.08 eV at multi reference configuration interaction/Aug‐cc‐pVQZ level of theory.

show abstract

Ω^{'' - bold1 / bold2} {bold-italicQ}^{'}^{(n)} = bold-italicJ Ω^{'' - bold1 / bold2} Q^{''} + D^{(bold-italicn)} n = ((), a, d)

where Ω ″ is a diagonal matrix of the vibrational frequencies of ground electronic state

({}, ω_{j}^{''})

d_{i}^{(n)}

) and is nonzero for the totally symmetric modes.…”

Section: Computational Details and Theoretical Considerationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Investigation of nonadiabatic coupling and diabatic electronic population dynamics on F₂O⁺ cation within multi reference configuration interaction calculations

Dehestani

2021

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

show abstract

“…In the Heisenberg picture, the normal coordinate with respect to excited state dynamics b has the form

Q_{i}^{' ((), b)} ((), τ) = e^{i {\overset{false^}{H}}_{b}^{0} τ / normalℏ} Q_{i}^{' ((), b)} e^{- i {\overset{false^}{H}}_{b}^{0} τ / normalℏ} = \frac{1}{2} Q_{i}^{' ((), b)} ((), e^{i {\overset{false˜}{ω}}_{i}^{' ((), b)} τ} - e^{- i {\overset{false˜}{ω}}_{i}^{' ((), b)} τ}) + \frac{1}{2 i {\overset{false˜}{ω}}_{i}^{' ((), b)}} P_{i}^{' ((), b)} ((), e^{i {\overset{false˜}{ω}}_{i}^{' ((), b)} τ} - e^{- i {\overset{false˜}{ω}}_{i}^{' ((), b)} τ}),

where

P_{i}^{' ((), b)}

is the conjugate momentum to normal coordinate

Q_{i}^{' ((), b)}

. We neglect rotation matrix and replace it with unit matrix in Equation , then we use Equation and obtain the nonadiabatic electronic population dynamics of 1 1 B 1 state which can be coupled with 1 1 A 2 state by nontotally symmetric mode b 2 for the displaced‐distorted harmonic oscillator model of O 3 using the following equation

\begin{matrix} true \\ P_{normalb}^{((), 2)} (t) = \exp (\int_{0}^{t} d t_{1} \{- Re \int_{0}^{t_{1}} d t_{2} e^{i ()} \end{matrix}

…”

Section: Theorymentioning

confidence: 99%

“…For describing adiabatic dynamics in CI, it is better that we use diabatic representation to eliminate the nonadiabatic coupling terms from the BO close‐coupling equations and replace by off‐diagonal electronic coupling terms. In this representation, coupling between the states is described by the off‐diagonal elements of the potential energy operator which are smooth functions of the nuclear coordinates even at the seam of degeneracies of the PESs . The adiabatic‐to‐diabatic transformation (ADT) matrix elements are found by integrating the coupled differential equations for the ADT angles along a two‐dimensional contour .…”

Section: Introductionmentioning

confidence: 99%

“…Borrelli and Peluso derived the electronic population dynamics using the second‐order cumulant approximation in the Liouville space for the displaced, distorted, and rotated PESs. We have derived general expression for electronic population at any time on systems involving a CI using time correlation function formalism for two vibronically coupled diabatic displaced‐distorted harmonic PESs . The purpose of this study is to determine electronic population dynamics of O 3 through CI using time correlation function formalism.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Nonadiabatic coupling and diabatic electronic population dynamics on 1¹A₂ and 1¹B₁ states of ozone molecule

Dehestani

2019

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

In this work, we examine nonadiabatic population dynamics for 1 1 B 1 and 1 1 A 2 states of ozone molecule (O 3 ). In O 3 , two lowest singlet excited states, 1 A 2 and 1 B 1 , can be coupled. Thus, population transfer between them occurs through the seam involving these two states. At any point of the seam (conical intersection), the Born-Oppenheimer approximation breaks down, and it is necessary to investigate nonadiabatic dynamics. We consider a linear vibronic coupling Hamiltonian model and evaluate vibronic coupling constant, diabatic frequencies for three modes of O 3 , bilinear and quadratic coupling constants for diabatic potentials, displacements, and Huang-Rhys coupling constants using ab initio calculations. The electronic structure calculations have been performed at the multireference configuration interaction and complete active space with second-order perturbation theory with a full-valence complete active space self-consistent field methods and augmented Dunning's standard correlation-consistent-polarized quadruple zeta basis set to determine ab initio potential energy surfaces for the ground state and first two excited states of O 3 , respectively. We have chosen active space comprising 18 electrons distributed over 12 active orbitals. Our calculations predict the linear vibronic coupling constant 0.123 eV. We have obtained the population on the 1 1 B 1 and 1 1 A 2 excited electronic states for the first 500 fs after photoexcitation.

show abstract

Non-adiabatic coupling in the potential energy surfaces of SO₂ molecule

Pourestarabadi,

Dehestani

2023

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

Effects of Displacement–Distortion of Potential Energy Surfaces on Nonadiabatic Electron Transfers via Conical Intersections: Application to SO₂ and trans-1,3,5-Hexatriene

Cited by 3 publications

References 67 publications

Investigation of nonadiabatic coupling and diabatic electronic population dynamics on F₂O⁺ cation within multi reference configuration interaction calculations

Investigation of nonadiabatic coupling and diabatic electronic population dynamics on F₂O⁺ cation within multi reference configuration interaction calculations

Nonadiabatic coupling and diabatic electronic population dynamics on 1¹A₂ and 1¹B₁ states of ozone molecule

Non-adiabatic coupling in the potential energy surfaces of SO₂ molecule

Contact Info

Product

Resources

About

Effects of Displacement–Distortion of Potential Energy Surfaces on Nonadiabatic Electron Transfers via Conical Intersections: Application to SO2 and trans-1,3,5-Hexatriene

Cited by 3 publications

References 67 publications

Investigation of nonadiabatic coupling and diabatic electronic population dynamics on F2O+ cation within multi reference configuration interaction calculations

Investigation of nonadiabatic coupling and diabatic electronic population dynamics on F2O+ cation within multi reference configuration interaction calculations

Nonadiabatic coupling and diabatic electronic population dynamics on 11A2 and 11B1 states of ozone molecule

Non-adiabatic coupling in the potential energy surfaces of SO2 molecule

Contact Info

Product

Resources

About

Effects of Displacement–Distortion of Potential Energy Surfaces on Nonadiabatic Electron Transfers via Conical Intersections: Application to SO₂ and trans-1,3,5-Hexatriene

Investigation of nonadiabatic coupling and diabatic electronic population dynamics on F₂O⁺ cation within multi reference configuration interaction calculations

Investigation of nonadiabatic coupling and diabatic electronic population dynamics on F₂O⁺ cation within multi reference configuration interaction calculations

Nonadiabatic coupling and diabatic electronic population dynamics on 1¹A₂ and 1¹B₁ states of ozone molecule

Non-adiabatic coupling in the potential energy surfaces of SO₂ molecule