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Table 1 Calculated and experimental values of the lowest energy optical transitions (eV) for hydrogen sulfide, bisulfide anion, poly-sulfide anions and sulfanes, using the 6-311+G(2d,p) basis (TD B3LYP results in italics, CIS oscillator strengths in parentheses)

From: Calculation of the visible-UV absorption spectra of hydrogen sulfide, bisulfide, polysulfides, and As and Sb sulfides, in aqueous solution

Molecule

ΔE CIS TD B3LYP

ΔE CIS COSMO

ΔE exp.

H2S

6.2, 6.7

6.4, 6.9

6.4, 6.7

 

5.9, 5.9

  

SH-

4.6

5.6

 
 

3.9

  

SH-···6H2O

5.6

5.8

5.4

 

4.3

  

S22-

1.9

3.3

 

S22-···4H2O

2.4

3.37 (0.023)

3.5

  

3.56 (0.025)

 
  

4.94 (0.060)

 

S32-

2.4

3.2

 

S32-···4H2O

2.8

3.22 (0.064)

3.0

  

4.23 (0.053)

 

S42-

3.0

3.6

 

S42-···4H2O

3.4

3.75a(0.027)

3.4

  

1.9

 
  

3.80 (0.006)

 
  

4.54 (0.027)

 

S42-··· 22H2Ob

3.6

-

 

S4H-

3.4

3.7

 

S4H-···4H20

3.7

3.8

 

S52-

3.17

3.55

3.3

S62-

3.25

3.54

-

S2H2

5.4

5.4

5.0

S3H2

5.2

 

4.5

 

4.2

  

S4H2

5.2

 

4.2

S5H2

5.1

 

4.1

  1. a3.64 and 3.62 eV for TD COSMO with 6-31 l+G(2d,p) and aug-cc-pVDZ bases, respectively. bONIOM calculation, with 6-311+G(2d,p) basis on S4 unit and 6-31G* basis on waters.