Electronic and mechanical anharmonicities in the vibrational spectra of the H-bonded, cryogenically cooled X - · HOCl (X=Cl, Br, I) complexes: Characterization of the strong anionic H-bond to an acidic OH group.

التفاصيل البيبلوغرافية
العنوان:	Electronic and mechanical anharmonicities in the vibrational spectra of the H-bonded, cryogenically cooled X ^- · HOCl (X=Cl, Br, I) complexes: Characterization of the strong anionic H-bond to an acidic OH group.
المؤلفون:	Stropoli SJ; Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA., Khuu T; Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA., Boyer MA; Department of Chemistry, University of Washington, Seattle, Washington 98195, USA., Karimova NV; Department of Chemistry, University of California Irvine, Irvine, California 92697, USA., Gavin-Hanner CF; Department of Chemistry, University of Washington, Seattle, Washington 98195, USA., Mitra S; Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA., Lachowicz AL; Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA., Yang N; Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA., Gerber RB; Department of Chemistry, University of California Irvine, Irvine, California 92697, USA., McCoy AB; Department of Chemistry, University of Washington, Seattle, Washington 98195, USA., Johnson MA; Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA.
المصدر:	The Journal of chemical physics [J Chem Phys] 2022 May 07; Vol. 156 (17), pp. 174303.
نوع المنشور:	Journal Article
اللغة:	English
بيانات الدورية:	Publisher: American Institute of Physics Country of Publication: United States NLM ID: 0375360 Publication Model: Print Cited Medium: Internet ISSN: 1089-7690 (Electronic) Linking ISSN: 00219606 NLM ISO Abbreviation: J Chem Phys Subsets: PubMed not MEDLINE; MEDLINE
أسماء مطبوعة:	Publication: New York, NY : American Institute of Physics Original Publication: Lancaster, Pa., American Institute of Physics.
مستخلص:	We report vibrational spectra of the H 2 -tagged, cryogenically cooled X ^- · HOCl (X = Cl, Br, and I) ion-molecule complexes and analyze the resulting band patterns with electronic structure calculations and an anharmonic theoretical treatment of nuclear motions on extended potential energy surfaces. The complexes are formed by "ligand exchange" reactions of X ^- · (H 2 O) n clusters with HOCl molecules at low pressure (∼10 ^-2 mbar) in a radio frequency ion guide. The spectra generally feature many bands in addition to the fundamentals expected at the double harmonic level. These "extra bands" appear in patterns that are similar to those displayed by the X ^- · HOD analogs, where they are assigned to excitations of nominally IR forbidden overtones and combination bands. The interactions driving these features include mechanical and electronic anharmonicities. Particularly intense bands are observed for the v = 0 → 2 transitions of the out-of-plane bending soft modes of the HOCl molecule relative to the ions. These involve displacements that act to break the strong H-bond to the ion, which give rise to large quadratic dependences of the electric dipoles (electronic anharmonicities) that drive the transition moments for the overtone bands. On the other hand, overtone bands arising from the intramolecular OH bending modes of HOCl are traced to mechanical anharmonic coupling with the v = 1 level of the OH stretch (Fermi resonances). These interactions are similar in strength to those reported earlier for the X ^- · HOD complexes.
تواريخ الأحداث:	Date Created: 20220507 Latest Revision: 20220509
رمز التحديث:	20240628
DOI:	10.1063/5.0083078
PMID:	35525657
قاعدة البيانات:	MEDLINE

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الوصف
تدمد:	1089-7690
DOI:	10.1063/5.0083078