Interference between Franck–Condon and Herzberg–Teller Terms in the Condensed-Phase Molecular Spectra of Metal-Based Tetrapyrrole Derivatives

Roy, Partha Pratim; Kundu, Sohang; Makri, Nancy; Fleming, Graham R.

doi:10.1021/acs.jpclett.2c01963

Interference between Franck–Condon and Herzberg–Teller Terms in the Condensed-Phase Molecular Spectra of Metal-Based Tetrapyrrole Derivatives

Journal Article · Fri Aug 05 00:00:00 EDT 2022 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.2c01963· OSTI ID:1896888

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Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy Nanoscience Institute (ENSI), Berkeley, California (United States)
Univ. of Illinois, Urbana, IL (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy Nanoscience Institute (ENSI), Berkeley, California (United States)s

The commonly used Franck-Condon (FC) approximation is inadequate for explaining the electronic spectra of compounds that possess vibrations with substantial Herzberg-Teller (HT) couplings. Metal-based tetrapyrrole derivatives, which are ubiquitous natural pigments, often exhibit prominent HT activity. In this paper, we compare the condensed phase spectra of zinc-tetraphenylporphyrin (ZnTPP) and zinc-phthalocyanine (ZnPc), which exhibit vastly different spectral features in spite of sharing a common tetrapyrrole backbone. The absorption and emission spectra of ZnTPP are characterized by a lack of mirror symmetry and nontrivial temperature dependence. In contrast, mirror symmetry is restored, and the nontrivial temperature-dependent features disappear in ZnPc. We attribute these differences to FC-HT interference, which is less pronounced in ZnPc because of a larger FC component in the dipole moment that leads to FC-dominated transitions. A single minimalistic FC-HT vibronic model reproduces all the experimental spectral features of these molecules. These observations suggest that FC-HT interference is highly susceptible to chemical modification.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1896888

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 32 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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