<p>Theoretical Study on Excited-State Proton Transfer via</p><p>Hydrogen-Bonded Ethanol (EtOH) wire for 7AI in the Gas</p><p>Phase Hua Fang* Department of Chemistry and Material Science, College of Science, Nanjing Forestry University, Nanjing 210037, People’s Republic of China Tel: +8 6 2585427621; Email: [email protected]</p><p>Supplementary</p><p>Figure SI Active space orbitals of transition state (TS) in the 7AI-EtOH complex obtained at the CASSCF/6-311g(d, p) level. A to E is the occupied orbital. F to I is the virtual orbital.</p><p>Figure SII Active space orbitals of transition state (TS1) in the 7AI-(EtOH)2 complex obtained at the CASSCF/6-311g(d, p) level. A to E is the occupied orbital. F to I is the virtual orbital.</p><p>Figure SIII Active space orbitals of transition state (TS2) in the 7AI-(EtOH)2 complex obtained at the CASSCF/6-311g(d, p) level. A to E is the occupied orbital. F to I is the virtual orbital.</p><p>−1 Figure SIV Normal mode of vibration with 116 cm of frequency in 7AI-(EtOH)2 at the CASSCF(10,9)/6-311G(d,p) level.</p><p>A B</p><p>C D</p><p>E F</p><p>G H</p><p>I Figure SI Active space orbitals of transition state (TS) in the 7AI-EtOH complex obtained at the CASSCF/6-311g(d, p) level. A to E is the occupied orbital. F to I is the virtual orbital.</p><p>A B</p><p>C D</p><p>E F</p><p>G H I</p><p>Figure SII Active space orbitals of transition state (TS1) in the 7AI-(EtOH)2 complex obtained at the CASSCF/6-311g(d, p) level. A to E is the occupied orbital. F to I is the virtual orbital.</p><p>A B</p><p>C D</p><p>E F</p><p>G H</p><p>I</p><p>Figure SIII Active space orbitals of transition state (TS2) in the 7AI-(EtOH)2 complex obtained at the CASSCF/6-311g(d, p) level. A to E is the occupied orbital. F to I is the virtual orbital. −1 Figure SIV Normal mode of vibration with 116 cm of frequency in 7AI-(EtOH)2 at the CASSCF(10,9)/6-311G(d,p) level.</p><p>It is clear that the excitation of this vibrational mode brings the correlation points</p><p> of H10, H17 and H23 close to those of the transition state; i.e., vibrational excitation of this mode shortens the reaction path to reach the transition state and hence speeds up the reaction probably by the enhanced tunneling. These results are consistent with the vibrational-mode specific nature of the ESTPT. </p>