Mechanical Forces Alter Conical Intersections Topology

  1. Rivero, D. 3
  2. Valentini, A. 23
  3. Fernández-González, M.A. 3
  4. Zapata, F. 3
  5. García-Iriepa, C. 13
  6. Sampedro, D. 1
  7. Palmeiro, R. 3
  8. Frutos, L.M. 3
  1. 1 Universidad de La Rioja

    Universidad de La Rioja

    Logroño, España


  2. 2 Università degli Studi di Siena

    Università degli Studi di Siena

    Siena, Italia


  3. 3 Universidad de Alcalá

    Universidad de Alcalá

    Alcalá de Henares, España


Journal of Chemical Theory and Computation

ISSN: 1549-9618

Year of publication: 2015

Volume: 11

Issue: 8

Pages: 3740-3745

Type: Article

DOI: 10.1021/ACS.JCTC.5B00375 SCOPUS: 2-s2.0-84938927373 GOOGLE SCHOLAR

More publications in: Journal of Chemical Theory and Computation


Cited by

  • Scopus Cited by: 10 (08-03-2023)
  • Web of Science Cited by: 10 (28-03-2023)

JCR (Journal Impact Factor)

  • Year 2015
  • Journal Impact Factor: 5.301
  • Journal Impact Factor without self cites: 4.354
  • Article influence score: 1.768
  • Best Quartile: Q1
  • Area: CHEMISTRY, PHYSICAL Quartile: Q1 Rank in area: 27/144 (Ranking edition: SCIE)
  • Area: PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Quartile: Q1 Rank in area: 5/35 (Ranking edition: SCIE)

SCImago Journal Rank

  • Year 2015
  • SJR Journal Impact: 2.702
  • Best Quartile: Q1
  • Area: Physical and Theoretical Chemistry Quartile: Q1 Rank in area: 7/172
  • Area: Computer Science Applications Quartile: Q1 Rank in area: 12/1558

Scopus CiteScore

  • Year 2015
  • CiteScore of the Journal : 9.4
  • Area: Computer Science Applications Percentile: 97
  • Area: Physical and Theoretical Chemistry Percentile: 92


Photoreactivity can be influenced by mechanical forces acting over a reacting chromophore. Nevertheless, the specific effect of the external forces in the photoreaction mechanism remains essentially unknown. Conical intersections are key structures in photochemistry, as they constitute the funnels connecting excited and ground states. These crossing points are well known to provide valuable information on molecular photoreactivity, including crucial aspects as potential photoproducts which may be predicted by just inspection of the branching plane vectors. Here, we outline a general framework for understanding the effect of mechanical forces on conical intersections and their implications on photoreactivity. Benzene S<inf>1</inf>/S<inf>0</inf> conical intersection topology can be dramatically altered by applying less than 1 nN force, making the peaked pattern of the intersection become a sloped one, also provoking the transition state in the excited state to disappear. Both effects can be related to an increase in the photostability as the conical intersection becomes more accessible, and its topology in this case favors the recovery of the initial reactant. The results indicate that the presence of external forces acting over a chromophore have to be considered as a potential method for photochemical reactivity control. © 2015 American Chemical Society.