LAUSR.org creates dashboard-style pages of related content for over 1.5 million academic articles. Sign Up to like articles & get recommendations!

Gas-phase thermochemistry of noncovalent ligand-alkali metal ion clusters: An impact of low frequencies.

Photo from wikipedia

The experimental gas-phase thermochemistry of reactions: M+ (S)n-1  + S → M+ (S)n and M+ + nS→ M+ (S)n , where M is an alkali metal and S is acetonitrile/ammonia, is reproduced. Three… Click to show full abstract

The experimental gas-phase thermochemistry of reactions: M+ (S)n-1  + S → M+ (S)n and M+ + nS→ M+ (S)n , where M is an alkali metal and S is acetonitrile/ammonia, is reproduced. Three approximations are tested: (1) scaled rigid-rotor-harmonic-oscillator (sRRHO); (2) the sRRHO(100) identical to (1), but with all vibrational frequencies smaller than 100 cm-1 replaced with 100 cm-1 ; (3) Grimme's modified scaled RRHO (msRRHO) (Grimme, Chem. Eur. J., 2012, 18, 9955-9964). The msRRHO approach provides the most accurate reaction entropies with the mean unsigned error (MUE) below 5.5 cal mol-1  K-1 followed by sRRHO(100) and sRRHO with MUEs of 7.2 and 16.9 cal mol-1  K-1 . For the first time, we propose using the msRRHO scheme to calculate the enthalpy contribution that is further utilized to arrive at reaction Gibbs free energies (∆Gr ) ensuring the internal consistency. The final ∆Gr MUEs for msRRHO, sRRHO(100) and sRRHO schemes are 1.2, 3.6 and 3.1 kcal mol-1 .

Keywords: gas phase; phase thermochemistry; alkali metal

Journal Title: Journal of computational chemistry
Year Published: 2023

Link to full text (if available)


Share on Social Media:                               Sign Up to like & get
recommendations!

Related content

More Information              News              Social Media              Video              Recommended



                Click one of the above tabs to view related content.