TY  - JOUR
A1  - Xiong, Tao
A1  - Saalfrank, Peter
T1  - Vibrationally Broadened Optical Spectra of Selected Radicals and Cations Derived from Adamantane: A Time-Dependent Correlation Function Approach
T2  - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory
N2  - Diamondoids are hydrogen-saturated molecular motifs cut out of diamond, forming a class of materials with tunable optoelectronic properties. In this work, we extend previous work on neutral, closed-shell diamondoids by computing with hybrid density functional theory and time-dependent correlation functions vibrationally broadened absorption spectra of cations and radicals derived from the simplest diamondoid, adamantane, namely, the neutral 1- and 2-adamantyl radicals (C10H15), the 1- and 2-adamantyl cations (C10H15+), and the adamantane radical cation (C10H16+). For selected cases, we also report vibrationally broadened emission, photoelectron, and resonance Raman spectra. Furthermore, the effect of the damping factor on the vibrational fine-structure is studied. The following trends are found: (1) Low-energy absorptions of the adamantyl radicals and cations, and of the adamantane cation, are all strongly red-shifted with respect to adamantane; (2) also, emission spectra are strongly red-shifted, whereas photoelectron spectra are less affected for the cases studied; (3) vibrational fine-structures are reduced compared to those of adamantane; (4) the spectroscopic signals of 1- and 2-adamantyl species are significantly different from each other; and (5) reducing the damping factor has only a limited effect on the vibrational fine-structure in most cases. This suggests that removing hydrogen atoms and/or electrons from adamantane leads to new optoelectronic properties, which should be detectable by vibronic spectroscopy.
Y1  - 2019
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/48019
SN  - 1089-5639
SN  - 1520-5215
VL  - 123
IS  - 41
SP  - 8871
EP  - 8880
PB  - American Chemical Society
CY  - Washington
ER  -