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Volumn 126, Issue 28, 2004, Pages 8823-8834

A fast photoswitch for minimally perturbed peptides: Investigation of the trans → cis photoisomerization of N-methylthioacetamide

Author keywords

[No Author keywords available]

Indexed keywords

GROUND STATE; INFRARED SPECTROSCOPY; ISOMERIZATION; POTENTIAL ENERGY; PROBABILITY;

EID: 3242667261     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja049227a     Document Type: Article
Times cited : (74)

References (48)
  • 14
    • 3242675119 scopus 로고    scopus 로고
    • note
    • Since the isomerization takes place about the formally single bond C-N, one should refer to s-trans-NMTAA and s-cis-NMTAA conformations. However, to conform to previous works, we use the labels cis or trans determined by the relative positions of the two NMTAA methyl groups.
  • 30
    • 3242704036 scopus 로고    scopus 로고
    • note
    • Energies and energy gaps oscillate during the geometry optimization and never converge, or if energy gap tends to converge the energy increases endlessly. This behavior has been found to be associated with highly sloped conical intersections.
  • 32
    • 3242694209 scopus 로고    scopus 로고
    • note
    • Since the irradiation wavelength can be changed without removing the sample from the FTIR spectrometer, the concentrations in photoequilibrium for different irradiation wavelengths can be determined with high accuracy (and independent of any spectrometer drifts) relative to the value at 255 nm by comparing the peak-to-peak differences in the FTIR-difference spectra shown in Figure 1d).
  • 33
    • 3242741015 scopus 로고    scopus 로고
    • note
    • Note, however, that the sample can be efficiently destroyed upon irradiation with an unfiltered low-pressure Hg lamp, which we attribute to excitation by light from the 193-nm line.
  • 36
    • 3242718605 scopus 로고    scopus 로고
    • note
    • T is the ratio of initially excited cis and trans molecules.
  • 39
    • 3242735704 scopus 로고    scopus 로고
    • note
    • -1 region, which can be easily subtracted as a linear background from the transient data. It stays constant at delay times longer than 100 ps, indicating the end of the main energy dissipation.
  • 41
    • 3242717702 scopus 로고    scopus 로고
    • note
    • 0 CASPT2 energy values reported in Table 5S in Supporting Information. Energy degeneracy was achieved at the CASSCF level of theory, but the CASPT2 treatment split the two energies. The mean values represent a good approximation of the energy of the CI.
  • 44
    • 3242657194 scopus 로고    scopus 로고
    • note
    • -1. See Table 5S in Supporting Information.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.