Role of Triplet States in the Photolysis of Proteogenic Amino Acids

Cristian Guerra, Yeray A. Rodríguez-Núñez, Adolfo E. Ensuncho

Research output: Contribution to journalArticlepeer-review

Abstract

This investigation delves into the UV photodissociation of pivotal amino acids (Alanine, Glycine, Leucine, Proline, and Serine) at 213 nm, providing insights into triplet-state deactivation pathways. Utilizing a comprehensive approach involving time-dependent density functional calculations (TD-DFT), multi-configurational methods, and ab-initio molecular dynamics (AIMD) simulations, we scrutinize the excited electronic states (T1, T2, and S1) subsequent to 213 nm excitation. Our findings demonstrate that α-carbonyl C−C bond-breaking in triplet states exhibits markedly lower barriers than in singlet states (below 5.0 kcal mol−1). AIMD simulations corroborate the potential involvement of triplet states in amino acid fragmentation, underscoring the significance of accounting for these states in photochemistry. Chemical bonding analyses unveil distinctive patterns for S1 and T1 states, with the asymmetric redistribution of electron density characterizing the C−C breaking in triplet states, in contrast to the symmetric breaking observed in singlet states. This research complements recent experimental discoveries, enhancing our comprehension of amino acid reactions in the interstellar medium.

Original languageEnglish
JournalChemPhysChem
DOIs
Publication statusAccepted/In press - 2023

Keywords

  • amino acids
  • C−C breaking
  • photodissociation
  • photolysis
  • triplet-state

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

Fingerprint

Dive into the research topics of 'Role of Triplet States in the Photolysis of Proteogenic Amino Acids'. Together they form a unique fingerprint.

Cite this