Jump to main content
Jump to site search

Issue 43, 2020
Previous Article Next Article

Vibrationally resolved valence and core photoionization and photoexcitation spectra of an electron-deficient trivalent boron compound: the case of catecholborane

Author affiliations

Abstract

Compounds containing trivalent boron (TB) as the electron-deficient site(s) find numerous practical uses ranging from Lewis bases in organic synthesis to high-tech industry, with a number of novel applications anticipated. We present an experimental and theoretical study of the gas-phase valence photoionization (VUV-PES), core photoionization (XPS) and photoexcitation (NEXAFS) spectra of a representative TB compound catecholborane (CB). For modelling and assigning the spectra we used the ΔDFT and restricted single excitation space TD-DFT methods for the XPS and NEXAFS, and OVGF and EOM-CCSD for the VUV-PES. The vibrationally resolved structure was computed in the Franck–Condon (FC) and Herzberg–Teller (FCHT) approximations generally resulting in a good agreement with the observed spectral features. For the prediction of core-electron binding energies (CEBEs) several density functionals were tested. The best performance overall was furnished by ωB97X-D suggesting that including the dispersion correction is beneficial. The FCHT vibronic intensities are in clear discrepancy with the B 1s NEXAFS spectrum if the harmonic approximation is used for the B–H wagging mode both in the ground and in the first core-excited state. Instead, a much better agreement is obtained if the excited state potential is approximated to a symmetric double-well. The observed vibronic pattern could be a general fingerprint of the presence of TB centre(s), specifically, the transfer of the (core) density to the vacant boron p-orbital in the excited state.

Graphical abstract: Vibrationally resolved valence and core photoionization and photoexcitation spectra of an electron-deficient trivalent boron compound: the case of catecholborane

Back to tab navigation

Supplementary files

Article information


Submitted
12 Sep 2020
Accepted
26 Oct 2020
First published
27 Oct 2020

Phys. Chem. Chem. Phys., 2020,22, 25396-25407
Article type
Paper

Vibrationally resolved valence and core photoionization and photoexcitation spectra of an electron-deficient trivalent boron compound: the case of catecholborane

I. Ljubić, M. T. Cvitaš, C. Grazioli, M. Coreno, S. Kazazić and I. Novak, Phys. Chem. Chem. Phys., 2020, 22, 25396
DOI: 10.1039/D0CP04822D

Social activity

Search articles by author

Spotlight

Advertisements