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Exploring hydrogen bond in the excited state leading toward intramolecular proton transfer: detailed analysis of the structure and charge density topology along the reaction path using QTAIM

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Abstract

Excited state intramolecular proton transfer (ESIPT) reaction along the O-H⋅⋅⋅⋅O hydrogen bond of o-hydroxy benzaldehyde (OHBA), methyl salicylate (MS) and salicylic acid (SA) was investigated by ab-initio quantum chemical calculation and theory of atoms and molecules (QTAIM) for the first time. Variation in several geometric as well as QTAIM parameters along the reaction coordinate was monitored in the fully relaxed excited state potential energy curve (PEC) obtained from intrinsic reaction coordinate (IRC) analysis. Although, the excited state barrier height for the forward reaction (∆E #0 ) reduces substantially in all the systems, MS and SA do not show any obvious asymmetry for proton transfer. For MS and SA, the crossover of the bond index as well as the lengths of the participating bonds at the saddle point is assigned due to this symmetry in accordance with bond energy – bond order (BEBO) model, which does not hold true in OHBA both in the ground and excited states. Bond ellipticity, covalent and metallic character were examined for different structures along the reaction path within the QTAIM framework. The QTAIM analysis was found to be able to uniquely distinguish between the ground and excited states of the OHBA molecule as well as both determining the effects on the bonding character of adding different substituent groups and differentiating between the ESIPT reactions in the SA and MS molecules.

In this paper, we report the dynamics and charge density topology of excited state intramolecular proton transfer (ESIPT) process in model systems like o-hydroxy benzaldehyde, salicylic acid and methyl salicylate using ab-initio quantum chemical calculation and also quantum theory of atoms and molecules (QTAIM) using fully relaxed excited state potential energy surface. The later technique has been used for the first time to explore the excited state process

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Acknowledgments

Thanks are due to Board of Research in Nuclear Sciences (BRNS) and Council of Scientific and Industrial Research (CSIR), Govt. of India for providing financial assistance to SM [project no. 2009/37/26/BRNS/1900] and AKC [project No. 01(2494)/11/EMR-II], respectively. The Hundred Talents Foundation of Hunan Province is gratefully acknowledged for the support of SJ and SRK.

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Authors and Affiliations

  1. Department of Chemistry, North-Eastern Hill University, Shillong, 793 022, India

    Sivaprasad Mitra, Asit K. Chandra & Pynsakhiat Miki Gashnga

  2. College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan, 410081, China

    Samantha Jenkins & Steven R. Kirk

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  1. Sivaprasad Mitra
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Correspondence to Sivaprasad Mitra or Samantha Jenkins.

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Fig. 1S

(A) Variation of different parameters during the E→K conversion for OHBA in the ground (a) and excited (b) states. The bond lengths and angles are designated by r and θ, respectively. The atom numbering is shown in Scheme 1. The variation of different parameters in the excited state of SA (B) and MS (C) are also shown (PPT 168 kb)

Fig. 1S

(PPT 165 kb)

Fig. 1S

(PPT 146 kb)

Fig. 1S

(PPT 146 kb)

Fig. 2S

The molecular graphs from QTAIM calculation of SA in the excited state. See caption of Fig. 3, for other details (PPT 586 kb)

Fig. 3S

The molecular graphs from QTAIM calculation of MS in the excited state. See caption of Fig. 3, for other details (PPT 513 kb)

Fig. 4S

The variation of the ratio |λ1|/λ3 with reaction pathway coordinate of different O-H and C-O BCPs in ground and excited sates (mentioned as GS and ES, respectively). See Scheme 1 for atom numbering (PPT 333 kb)

Fig. 5S

The variation of H(r b) with reaction pathway coordinate of different O-H and C-O bonds in ground and excited sates (mentioned as GS and ES, respectively). See Scheme 1 for atom numbering (PPT 349 kb)

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Mitra, S., Chandra, A.K., Gashnga, P.M. et al. Exploring hydrogen bond in the excited state leading toward intramolecular proton transfer: detailed analysis of the structure and charge density topology along the reaction path using QTAIM. J Mol Model 18, 4225–4237 (2012). https://doi.org/10.1007/s00894-012-1408-1

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