Interstate vibronic coupling constants between electronic excited states for complex molecules
Interstate vibronic coupling constants between electronic excited states for complex molecules
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DOI：
10.1063/1.5022760
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发表时间：
2018-03-28
影响因子：
4.4
通讯作者：
Gindensperger, Etienne
中科院分区：
文献类型：
--
作者：
Fumanal, Maria;Plasser, Felix;Gindensperger, Etienne
在构造分子激发态流形中量子动力学的非绝热振动哈密顿量时，耦合常数通常仅从激发态能量信息中提取。本文采用一种新的协议，通过激发态绝热辅助波函数之间的重叠积分，在时间依赖的密度泛函理论水平上获得州际振动耦合常数。我们讨论了这种方法的优点及其未来应用于复杂系统的潜力，特别是那些多个电子态在能量上紧密相连并相互作用的系统。我们将该协议应用于原型铼羰基配合物[Re(CO)(3)(N，N)(L)]（N +）的研究，最近报道了线性振动耦合模型内包括自旋-轨道耦合的非绝热量子动力学。AIP出版社出版。
In the construction of diabatic vibronic Hamiltonians for quantum dynamics in the excited-state manifold of molecules, the coupling constants are often extracted solely from information on the excited-state energies. Here, a new protocol is applied to get access to the interstate vibronic coupling constants at the time-dependent density functional theory level through the overlap integrals between excited-state adiabatic auxiliary wavefunctions. We discuss the advantages of such method and its potential for future applications to address complex systems, in particular, those where multiple electronic states are energetically closely lying and interact. We apply the protocol to the study of prototype rhenium carbonyl complexes [Re(CO)(3)(N,N)(L)](n+) for which non-adiabatic quantum dynamics within the linear vibronic coupling model and including spin-orbit coupling have been reported recently. Published by AIP Publishing.