Metrics
13 Record Views
Journal article
Theoretical Analysis of the n 1 ν 1 + ν 3 Combination Bands in Hydrogen Bihalide Anions, XHX - , X = {F, Cl, Br, and I}
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.129(47), pp.10848-10858
11/14/2025
PMID: 41237405
Web of Science ID: WOS:001615255600001
Abstract
The anharmonic vibrational structures of XHX⁻ anions, X = {F, Cl, Br, and I}, were examined with a focus on the n₁v₁+v₃ combination bands, where
is the excitation quanta of the symmetric X-H stretch (v₁) and v₃is the asymmetric X-H stretch. Full-dimensional potential energy surfaces (PESs) were built by using a multilevel scheme based on CCSD(T) and MP2 levels of theories. These dual-level PESs were then used to simulate the anharmonic spectra and to assess the extent of vibrational coupling. The vibrational signatures of XHX⁻ are very similar to those of the previously studied proton-bound noble gas dimers. The combination bands become more visible as the halide becomes heavier. The quantum nature of these combination bands was examined using an adiabatic model. Furthermore, the halide binding energies for XHX⁻ , X = {F, Cl, Br, and I}, were studied using a modern fragmentation-based method, energy decomposition analysis based on absolutely localized molecular orbitals (ALMO-EDA). The halide binding energy decreases from that of FHF⁻ to that of IHI⁻. Both the geometric distortion and dispersion-free frozen components destabilize these complexes, weakening their binding energies. However, the dispersion, polarization effects, and charge transfer contributions stabilize these complexes.
Files and links (2)
theoretical-analysis-of-the-n1ν1-ν3-combination-bands-in-hydrogen-bihalide-anions-xhx-x-f-cl-br-and-i2.37 MB
CC BY V4.0, Open Access
Related links
Details
- Title
- Theoretical Analysis of the n 1 ν 1 + ν 3 Combination Bands in Hydrogen Bihalide Anions, XHX - , X = {F, Cl, Br, and I}
- Publication Details
- The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.129(47), pp.10848-10858
- Resource Type
- Journal article
- Publisher
- American Chemical Society; WASHINGTON
- Number of pages
- 11
- Grant note
- Ministry of Science and Technology, Taiwan: MOST105-2113-M-001-006
Various grants from Academia Sinica and the Ministry of Science and Technology (MOST) of Taiwan under Grant Nos. MOST105-2113-M-001-006, MOST106-2113-M-001-005, MOST106-2113-M-152-001, MOST107-2113-M-152-001, MOST107-2628-M-001-002-MY4, MOST109-2639-M-009-001-ASP, MOST109-2113-M-001-040, and MOST108-2113-M-001-028-MY3 financially supported this work. Computational resources are partly supported by Academia Sinica and the National Center for High-Performance Computing (NCHC) of Taiwan. We wish to thank Dr. Qian-Rui Huang for the NMR scanner and DVR solver.
- Copyright
- © 2025 The Authors.
- Identifiers
- WOS:001615255600001; 99381548016606600
- Academic Unit
- Chemistry; Hal Marcus College of Science and Engineering
- Language
- English