Relative energies among S3 intermediates in the photosystem II revealed by DLPNO coupled cluster and hybrid DFT calculations. Possible pathways of water insertion in the S2 to S3 transition

Koichi Miyagawa ^a,*, Mitsuo Shoji ^a, Hiroshi Isobe ^b, Takashi Kawakami ^c,d,*, Takahito Nakajima ^d, Kizashi Yamaguchi ^d,e,f,*

a Center of Computational Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8577, Japan

b Graduate School of Natural Science and Technology, Okayama University, Okayama 700-8530, Japan

c Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan

d RIKEN Center for Computational Science, Kobe, Hyogo 650-0047, Japan

e The Institute of Scientific and Industrial Research, Osaka University, Ibaraki 567-0047, Japan

f Center for Quantum Information and Quantum Biology (QIQB), Osaka University, Toyonaka, Osaka 560-0043, Japan