Pregled bibliografske jedinice broj: 1091121
Vibrationally resolved valence and core photoionization and photoexcitation spectra of an electron-deficient trivalent boron compound: the case of catecholborane
Vibrationally resolved valence and core photoionization and photoexcitation spectra of an electron-deficient trivalent boron compound: the case of catecholborane // PCCP. Physical chemistry chemical physics, 22 (2020), 25396-25407 doi:10.1039/D0CP04822D (međunarodna recenzija, članak, znanstveni)
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Naslov
Vibrationally resolved valence and core
photoionization and photoexcitation spectra of an
electron-deficient trivalent boron compound: the
case of catecholborane
Autori
Ljubić, Ivan ; Cvitaš, Marko Tomislav ; Grazioli, Cesare ; Coreno, Marcello ; Kazazić, Saša ; Novak, Igor
Izvornik
PCCP. Physical chemistry chemical physics (1463-9076) 22
(2020);
25396-25407
Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni
Ključne riječi
VUV-PES spectra ; XPS spectra ; NEXAFS spectra ; Vibrationally Resolved Spectra ; DFT ; TDDFT ; Trivalent Boron ; Catecholborane
Sažetak
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.
Izvorni jezik
Engleski
Znanstvena područja
Kemija
POVEZANOST RADA
Projekti:
IP-2014-09-7540 - Novo poglavlje u procesima prijenosa naboja u vodenim otopinama (CTPAMR) (Ljubić, Ivan, HRZZ - 2014-09) ( CroRIS)
Ustanove:
Institut "Ruđer Bošković", Zagreb
Citiraj ovu publikaciju:
Časopis indeksira:
- Current Contents Connect (CCC)
- Web of Science Core Collection (WoSCC)
- Science Citation Index Expanded (SCI-EXP)
- SCI-EXP, SSCI i/ili A&HCI
- Scopus
- MEDLINE