Spectral shifts and helium configurations in 4He(N)-tetracene clusters.
Spectral shifts of electronic transitions of tetracene in helium droplets are investigated in a theoretical study of (4)He(N)-tetracene clusters with 1 < or = N < or = 150. Utilizing a pairwise interaction for the S(0) state of tetracene with helium that is extended by semiempirical terms to construct a potential for the S(1) state of tetracene with helium, the spectral shift is calculated from path integral Monte Carlo calculations of the helium equilibrium properties with tetracene in the S(0) and S(1) states at T = 0 and at T = 0.625 K. The calculated spectral shifts are in quantitative agreement with available experimental measurements for small values of N (< or = 8) at T approximately 0.4 K and show qualitative agreement for larger N (10-20). The extrapolated value of the spectral shift in large droplets (N approximately 10(4)) is approximately 90% of the experimentally measured value. We find no evidence of multiple configurations of helium for any cluster size for either the S(0) or S(1) state of tetracene. These results suggest that the observed spectral splitting of electronic transitions of tetracene in large helium droplets is not due to the coexistence of static metastable helium densities, unlike the situation previously analyzed for the phthalocyanine molecule.
Whitley
Heather D
HD
Department of Chemistry and Kenneth S. Pitzer Center for Theoretical Chemistry, University of California, Berkeley, California 94720, USA. whitley3@llnl.gov
DuBois
Jonathan L
JL
Whaley
K Birgitta
KB