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Multi-dimensional quantum mechanical simulations are carried out to understand the multi-state and multi-mode vibronic interactions in the first six low-lying viz., X ̃ 2 B 1 , A ̃ 2 A 1 , B ̃ 2 B 2 , C ̃ 2 A 2 , D ̃ 2 A 1 , and E ̃ 2 B 1 electronic states of c-C2H4O·+. Vibronic coupling theory is applied to study interactions among electronic states using symmetry selection rules. A model 6 × 6 diabatic electronic Hamiltonian is constructed. The parameters of the diabatic Hamiltonian are estimated by performing extensive ab initio electronic structure calculations, using the EOM-IP-CCSD method. The nuclear dynamics calculations are performed with both time-independent and time-dependent quantum mechanical methods. The calculated vibronic structures of six electronic states are found to be in excellent agreement with the available experimental findings. Progressions found in the theoretical spectrum are assigned in terms of vibrational modes. It is found that extremely strong vibronic interactions among the X ̃ 2 B 1 – A ̃ 2 A 1 , B ̃ 2 B 2 – C ̃ 2 A 2 , and D ̃ 2 A 1 – E ̃ 2 B 1 electronic states results into highly overlapping vibronic bands due to multiple multi-state conical intersections. The impact of associated nonadiabatic effects on the vibronic structure and dynamics of the mentioned electronic states is examined at length. Interesting comparison is made with the results obtained for the isomeric acetaldehyde radical cation. [ABSTRACT FROM AUTHOR]

In this article, the theoretical photoionization spectroscopy of the aziridine (C2H5N) molecule is investigated. To start with, we have optimized the geometry of this molecule at the neutral electronic ground state at the density functional theory/augmented correlation-consistent polarized valence triple zeta level of theory using the G09 program. The electronic structure calculations were restricted to the first six low-lying electronic states in order to account for the experimental photoelectron spectrum of the C2H5N molecule. The first six low-lying electronic states ( X ̃ 2 A ′ , A ̃ 2 A ′ , B ̃ 2 A ″ , C ̃ 2 A ″ , D ̃ 2 A ′ , and E ̃ 2 A ′ ) of the potential energy surfaces (PESs) are calculated by both equation of motion-ionization potential-coupled cluster singles and doubles and multi-configuration quasi-degenerate perturbation theory ab initio quantum chemistry methods along the dimensionless normal displacement coordinates in which multiple conical intersections were established among the considered electronic states. A (6 × 6) model vibronic Hamiltonian is constructed on a diabatic electronic basis, using the symmetry selection rules and Taylor series expansion. The Cs symmetry point group of the aziridine molecule leads to electronic states symmetry of either A′ or A″, and these states are close in energy, due to which the same symmetry electronic states avoid each other. To get a smooth diabatic PES, a fourfold diabatization scheme is used, which is implemented in the General Atomic and Molecular Electronic Structure Systems suite of programs. All the parameters used in the diabatic vibronic coupling model Hamiltonian are calculated in terms of the normal modes of vibrational coordinates. Finally, the vibronic model Hamiltonian constructed for the coupled six electronic states is used to solve both time-independent and time-dependent Schrödinger equations using the multi-configuration time-dependent Hartree program module to obtain the dynamical observables. The theoretical vibronic band structure is found to be in good accord with the available experimental results. [ABSTRACT FROM AUTHOR]

Vibronic coupling in the first eight electronic excited states of Pentafluorobenzene (PFBz) is investigated in this article. In particular, the vibronic coupling between the optically bright ππ* and optically dark πσ* states of PFBz is considered. A model 8 × 8 diabatic Hamiltonian is constructed in terms of normal coordinate of vibrational modes using the standard vibronic coupling theory and symmetry selection rule. The Hamiltonian parameters are estimated with the aid of extensive ab initio quantum chemistry calculations. The topography of the first eight electronic excited states of PFBz is examined at length, and multiple multi-state conical intersections are established. The nuclear dynamics calculations on the coupled electronic surfaces are carried out from first principles by the wave packet propagation method. Theoretical results are found to be in good accord with the available experimental optical absorption spectrum of PFBz. [ABSTRACT FROM AUTHOR]

Nuclear dynamics in the first six vibronically coupled electronic states of pentafluorobenzene radical cation is studied with the aid of the standard vibronic coupling theory and quantum dynamical methods. A model 6 × 6 vibronic Hamiltonian is constructed in a diabatic electronic basis using symmetry selection rules and a Taylor expansion of the elements of the electronic Hamiltonian in terms of the normal coordinate of vibrational modes. Extensive ab initio quantum chemistry calculations are carried out for the adiabatic electronic energies to establish the diabatic potential energy surfaces and their coupling surfaces. Both time-independent and time-dependent quantum mechanical methods are employed to perform nuclear dynamics calculations. The vibronic spectrum of the electronic states is calculated, assigned, and compared with the available experimental results. Internal conversion dynamics of electronic states is examined to assess the impact of various couplings on the nuclear dynamics. The impact of increasing fluorination of the parent benzene radical cation on its radiative emission is examined and discussed. [ABSTRACT FROM AUTHOR]

We report photo-isomerization of malonaldehyde in its electronic ground state (S0), mediated by coupled 1nπ*(S1)–1ππ*(S2) excited electronic states, accomplished with the aid of optimally designed ultraviolet (UV)-laser pulses. In particular, control of H-transfer from a configuration predominantly located in the left well (say, reactant) to that in the right well (say, product) of the electronic ground S0 potential energy surface is achieved by a pump–dump mechanism including the nonadiabatic interactions between the excited S1 and S2 states. An interplay between the nonadiabatic coupling due to the conical intersection of the S1 and S2 states and the laser–molecule interaction is found to be imprinted in the time-dependent electronic population. The latter is also examined by employing optimal fields of varying intensities and frequencies of the UV laser pulses. For the purpose of the present study, we constructed a three-state and two-mode coupled diabatic Hamiltonian with the help of adiabatic electronic energies and transition dipole moments calculated by ab initio quantum chemistry methods. The electronic diabatic model is developed using the calculated adiabatic energies of the two excited electronic states (S1 and S2) in order to carry out the dynamics study. The optimal fields for achieving the controlled isomerization are designed within the framework of optimal control theory employing the optimization technique of a multitarget functional using the genetic algorithm. The laser-driven dynamics of the system is treated by numerically solving the time-dependent Schrödinger equation within the dipole approximation. A time-averaged yield of the target product of ∼40% is achieved in the present treatment of dynamics with optimal laser pulses. [ABSTRACT FROM AUTHOR]

We report photo-isomerization of malonaldehyde in its electronic ground state (S0), mediated by coupled 1nπ*(S1)-1ππ*(S2) excited electronic states, accomplished with the aid of optimally designed ultraviolet (UV)-laser pulses. In particular, control of H-transfer from a configuration predominantly located in the left well (say, reactant) to that in the right well (say, product) of the electronic ground S0 potential energy surface is achieved by a pump-dump mechanism including the nonadiabatic interactions between the excited S1 and S2 states. An interplay between the nonadiabatic coupling due to the conical intersection of the S1 and S2 states and the laser-molecule interaction is found to be imprinted in the time-dependent electronic population. The latter is also examined by employing optimal fields of varying intensities and frequencies of the UV laser pulses. For the purpose of the present study, we constructed a three-state and two-mode coupled diabatic Hamiltonian with the help of adiabatic electronic energies and transition dipole moments calculated by ab initio quantum chemistry methods. The electronic diabatic model is developed using the calculated adiabatic energies of the two excited electronic states (S1 and S2) in order to carry out the dynamics study. The optimal fields for achieving the controlled isomerization are designed within the framework of optimal control theory employing the optimization technique of a multitarget functional using the genetic algorithm. The laser-driven dynamics of the system is treated by numerically solving the time-dependent Schrödinger equation within the dipole approximation. A time-averaged yield of the target product of ∼40% is achieved in the present treatment of dynamics with optimal laser pulses.