On the Importance of Well-Defined Thermal Correlation Functions in Simulating Vibronic Spectra

التفاصيل البيبلوغرافية
العنوان: On the Importance of Well-Defined Thermal Correlation Functions in Simulating Vibronic Spectra
المؤلفون: Rami Gherib, Scott N. Genin, Ilya G. Ryabinkin
المصدر: The Journal of Physical Chemistry A. 126:3947-3956
بيانات النشر: American Chemical Society (ACS), 2022.
سنة النشر: 2022
مصطلحات موضوعية: Chemical Physics (physics.chem-ph), Physics - Chemical Physics, FOS: Physical sciences, Physical and Theoretical Chemistry
الوصف: Two difficulties associated with the computations of thermal vibrational correlation functions are discussed. The first one is the lack of a well-behaved expression that is valid at both high-temperature and $T \to 0$ K limits. Specifically, if the partition function and the propagator are considered separately, then thermal vibrational correlation functions may have an indeterminate form 0/0 in the limit $T \to 0$ K. This difficulty is resolved when the partition function and the propagator are jointly considered in the harmonic approximation, which allows a problematic term that emanates from the zero-point energy to be cancelled out thereby producing a thermal correlation function with a determinate form in $T \to 0$ K limit. The second difficulty is related to the multivaluedness of the vibrational correlation function. We show numerically that an improper selection of branch leads to discontinuities in the computed correlation function and an incorrect vibronic spectra. We propose a phase tracking procedure that ensures continuity of both real and imaginary parts of the correlation function to recover the correct spectra. We support our findings by simulating the UV-vis absorption spectra of pentacene at 4 K and benzene at 298 K. Both are found to be in good agreement with their experimental counterparts.
تدمد: 1520-5215
1089-5639
URL الوصول: https://explore.openaire.eu/search/publication?articleId=doi_dedup___::6546a06595d007c1d02be09f9350564d
https://doi.org/10.1021/acs.jpca.2c02219
حقوق: OPEN
رقم الأكسشن: edsair.doi.dedup.....6546a06595d007c1d02be09f9350564d
قاعدة البيانات: OpenAIRE