We prepared the first cis-trans dimer of formic acid and measured its vibrational spectrum in a low-temperature Ar matrix. This preparation was done by selective vibrational excitation of the trans-trans noncyclic dimer. It was found that the stability of the cis-trans dimer against proton tunneling is strongly improved compared to the monomer, especially at elevated temperatures (>30 K). This surprising phenomenon was explained by differences in dynamical, energetic, and vibrational properties of the dimer and monomer. The obtained results show that the proton tunneling reactions can be strongly modified in the hydrogen-bonded solid network compared to the monomeric species.

Download full-text PDF

Source
http://dx.doi.org/10.1021/ja064154bDOI Listing

Publication Analysis

Top Keywords

proton tunneling
12
formic acid
8
cis-trans dimer
8
dimer
5
cis-trans formic
4
acid dimer
4
dimer experimental
4
experimental observation
4
observation improved
4
improved stability
4

Similar Publications

Constrained Nuclear-Electronic Orbital Transition State Theory Using Energy Surfaces with Nuclear Quantum Effects.

J Chem Theory Comput

January 2025

Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.

Hydrogen-atom transfer is crucial in a myriad of chemical and biological processes, yet the accurate and efficient description of hydrogen-atom transfer reactions and kinetic isotope effects remains challenging due to significant quantum effects on hydrogenic motion, especially tunneling and zero-point energy. In this paper, we combine transition state theory (TST) with the recently developed constrained nuclear-electronic orbital (CNEO) theory to propose a new transition state theory denoted CNEO-TST. We use CNEO-TST with CNEO density functional theory (CNEO-DFT) to predict reaction rate constants for two prototypical gas-phase hydrogen-atom transfer reactions and their deuterated isotopologic reactions.

View Article and Find Full Text PDF

Proton-coupled electron transfer (PCET) is a fundamental redox process and has clear advantages in selectively activating challenging C-H bonds in many biological processes. Intrigued by this activation process, we aimed to develop a facile PCET process in cancer cells by modulating proton tunneling. This approach should lead to the design of an alternative photodynamic therapy (PDT) that depletes the mitochondrial electron transport chain (ETC), the key redox regulator in cancer cells under hypoxia.

View Article and Find Full Text PDF

Large amplitude motions (LAMs), most notably represented by proton tunneling, mark a significant departure from small amplitude vibrations where protons merely oscillate around their equilibrium positions. These substantial displacements require tunneling through potential energy barriers, leading to splittings in, e.g.

View Article and Find Full Text PDF

Hydride-Induced Reconstruction of Pd Electrode Surfaces: A Combined Computational and Experimental Study.

Adv Mater

December 2024

Physics of Energy Conversion and Storage, Department of Physics, Technical University of Munich, James-Franck-Straße 1, 85748, Garching, Germany.

Designing electrocatalysts with optimal activity and selectivity relies on a thorough understanding of the surface structure under reaction conditions. In this study, experimental and computational approaches are combined to elucidate reconstruction processes on low-index Pd surfaces during H-insertion following proton electroreduction. While electrochemical scanning tunneling microscopy clearly reveals pronounced surface roughening and morphological changes on Pd(111), Pd(110), and Pd(100) surfaces during cyclic voltammetry, a complementary analysis using inductively coupled plasma mass spectrometry excludes Pd dissolution as the primary cause of the observed restructuring.

View Article and Find Full Text PDF

Dynamics and mechanism of DNA repair by a bifunctional cryptochrome.

Proc Natl Acad Sci U S A

December 2024

Center for Ultrafast Science and Technology, School of Chemistry and Chemical Engineering, School of Physics and Astronomy, Zhang Jiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai 200240, China.

Photolyase and cryptochrome belong to a group of structurally similar flavoproteins but with two distinct functions of DNA repair as a photoenzyme and signal transduction as a photoreceptor, respectively, under blue-light illumination. Here, we studied a recently discovered bifunctional cryptochrome (CraCRY) with focus on its repair of UV-induced pyrimidine-pyrimidone (6-4) photoproduct (6-4PP). We used femtosecond spectroscopy and site-directed mutagenesis to map out the critical elementary steps by following the dynamics of initial reactants, various intermediates, and final products.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!