Nonlinear Molecular Electronic Spectroscopy via MCTDH Quantum Dynamics: From Exact to Approximate Expressions

• Published in: Journal of chemical theory and computation Vol. 19; no. 7; pp. 2075 - 2091
• Main Authors: Segatta, Francesco, Ruiz, Daniel Aranda, Aleotti, Flavia, Yaghoubi, Martha, Mukamel, Shaul, Garavelli, Marco, Santoro, Fabrizio, Nenov, Artur
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 11.04.2023
• Subjects: Approximation; Computation; Electromagnetic fields; Electronic structure; Hamiltonian functions; Hamiltonians; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Line spectra; Nonlinear optics; Potential energy; Quantum mechanics; Quantum theory; Response functions; Spectroscopy; Spectroscopy and Excited States; Spectrum analysis; Time dependence; Wave packets; Wave propagation
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/acs.jctc.2c01059

We present an accurate and efficient approach to computing the linear and nonlinear optical spectroscopy of a closed quantum system subject to impulsive interactions with an incident electromagnetic field. It incorporates the effect of ultrafast nonadiabatic dynamics by means of explicit numerical propagation of the nuclear wave packet. The fundamental expressions for the evaluation of first- and higher-order response functions are recast in a general form that can be used with any quantum dynamics code capable of computing the overlap of nuclear wave packets evolving in different states. Here we present the evaluation of these expressions with the multiconfiguration time-dependent Hartree (MCTDH) method. Application is made to pyrene, excited to its lowest bright excited state S 2 which exhibits a sub-100-fs nonadiabatic decay to a dark state S 1. The system is described by a linear vibronic coupling Hamiltonian, parametrized with multiconfiguration electronic structure methods. We show that the ultrafast nonadiabatic dynamics can have a remarkable effect on the spectral line shapes that goes beyond simple lifetime broadening. Furthermore, a widely employed approximate expression based on the time scale separation of dephasing and population relaxation is recast in the same theoretical framework. Application to pyrene shows the range of validity of such approximations.