Conformational and structural stability of n and 2-propylthiols: a revisit

Abstract

C–C and C–S bond rotations give four minima for nP molecules. Computational predictions reinforced by ESPM, MCA, NBO, FMO and NCI analyses excellently matched with experimental results.

Nature and Strength of Sulfur-Centered Hydrogen Bond in Methanethiol Aqueous Solutions

“…In this context, Laplacian electron density and total electron density play crucial role in the assessment of the inter or intramolecular interactions. Majorly, the electron density [ρ­(r)] and its Laplacian electron density [▽ 2 ρ­(r)] play a significant role in characterizing the hydrogen bond, and thus, we completed AIM calculations for our system to clarify the precise nature of the interactions …”

“…Generally, the H–L gap measures the system’s stability in terms of chemical hardness or global softness. Hardness of a system is linearly dependent on the values of the H–L gaps . The computed results of different energy parameters of the FMO analysis are given in Table S5 and Figure S3.…”

“…Corresponding to low-energy conformers, electrostatic potential charge, noncovalent interaction (NCI) representation, AIM analysis, NBO analysis, and FMO calculations were carried out, and global reactivity terms such as the chemical potential (μ), hardness (η), electrophilicity index (ω), global softness ( S ), and electronegativity (χ) were obtained at the B3LYP-D3/aug-cc-pVQZ level of theory . LED analysis was formed to check the physical behavior of the contributor of the IE. − MultiWFN software was used for NCI and AIM calculations with the wavefunctions generated from the Gaussian 16 computational suite.…”

“…Majorly, the electron density [ρ(r)] and its Laplacian electron density [▽ 2 ρ(r)] play a significant role in characterizing the hydrogen bond, and thus, we completed AIM calculations for our system to clarify the precise nature of the interactions. 22 As per Koch and Popelier predictions, bond critical points (BCPs) elucidate the path of the hydrogen bonds where the value of ρ(r) lies in the range from 0.002 to 0.040 au and ▽ 2 ρ(r) in the range from 0.024 to 0.139 au 33−36 The calculated parameters of BCP of (3, −1) are given in Table S4, and their corresponding basin surfaces are shown in Figure 2. For the systems studied herein, it was found that both ▽ 2 ρ(r) and ρ(r) exhibited the following trend for the O−H−O > S− H−S > O−H−S > S−H−O hydrogen bonds.…”

“…Hardness of a system is linearly dependent on the values of the H−L gaps. 22 The computed results of different energy parameters of the FMO analysis are given in Table S5 and Figure S3. The H−L gaps for the water-only cluster were much larger (refer Table S5), implying that the water cluster was the most stable compared to methanethiol-only and mixed clusters.…”