Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation

• Published in: The Journal of chemical physics 2019-05, Vol.150 (19), p.194110-194110
• Main Authors: Cotton, Stephen J., Miller, William H.
• Format: Article
• Language: English
• Subjects: Degrees of freedom; Molecular dynamics; Parameter modification; Photodissociation; Physics; Potential energy; Trajectories; Zero point energy
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.5094458

An electronic zero-point energy (ZPE) adjustment protocol is presented within the context of the symmetrical quasiclassical (SQC) quantization of the electronic oscillator degrees of freedom (DOF) in classical Meyer-Miller (MM) vibronic dynamics for the molecular dynamics treatment of electronically nonadiabatic processes. The “adjustment” procedure maintains the same initial and final distributions of coordinates and momenta in the electronic oscillator DOF as previously given by the SQC windowing protocol but modifies the ZPE parameter in the MM Hamiltonian, on a per trajectory basis, so that the initial nuclear forces are precisely those corresponding to the initial electronic quantum state. Examples demonstrate that this slight modification to the standard SQC/MM approach significantly improves treatment of the multistate nonadiabatic dynamics following a Franck-Condon type vertical excitation onto a highly repulsive potential energy surface as is typical in the photodissociation context.