Selected ATcT [1, 2] enthalpy of formation based on version 1.148 of the Thermochemical Network [3]

This version of ATcT results[3] was generated by additional expansion of version 1.140 to include species relevant to a recent study of the role of atmospheric methanediol[4].

Thioformaldehyde cation

Formula: [CH2S]+ (g)

CAS RN: 61356-81-8

ATcT ID: 61356-81-8*0

SMILES: C=[S+]

InChI: InChI=1S/CH2S/c1-2/h1H2/q+1

InChIKey: PITNAJWFZQWKRG-UHFFFAOYSA-N

Hills Formula: C1H2S1+

2D Image:

Aliases: [CH2S]+; Thioformaldehyde cation; Thioformaldehyde ion (1+); CH2S+

Relative Molecular Mass: 46.0920 ± 0.0061

Δ_fH°(0 K)	Δ_fH°(298.15 K)	Uncertainty	Units
1025.9	1022.3	± 2.0	kJ/mol

3D Image of [CH2S]+ (g)

spin ON spin OFF

Top contributors to the provenance of Δ_fH° of [CH2S]+ (g)

The 12 contributors listed below account for 91.3% of the provenance of Δ_fH° of [CH2S]+ (g).

Please note: The list is limited to 20 most important contributors or, if less, a number sufficient to account for 90% of the provenance. The Reference acts as a further link to the relevant references and notes for the measurement. The Measured Quantity is normaly given in the original units; in cases where we have reinterpreted the original measurement, the listed value may differ from that given by the authors. The quoted uncertainty is the a priori uncertainty used as input when constructing the initial Thermochemical Network, and corresponds either to the value proposed by the original authors or to our estimate; if an additional multiplier is given in parentheses immediately after the prior uncertainty, it corresponds to the factor by which the prior uncertainty needed to be multiplied during the ATcT analysis in order to make that particular measurement consistent with the prevailing knowledge contained in the Thermochemical Network.

Contribution (%)	TN ID	Reaction	Measured Quantity	Reference
13.3	9325.4	CH2S (g, singlet) + CH3OH (g) → CH3SH (g) + CH2O (g, singlet)	Δ_rH°(0 K) = -12.08 ± 1.2 kcal/mol	Ruscic W1RO
11.3	9325.2	CH2S (g, singlet) + CH3OH (g) → CH3SH (g) + CH2O (g, singlet)	Δ_rH°(0 K) = -11.47 ± 1.3 kcal/mol	Ruscic G4
9.7	9325.1	CH2S (g, singlet) + CH3OH (g) → CH3SH (g) + CH2O (g, singlet)	Δ_rH°(0 K) = -11.32 ± 1.4 kcal/mol	Ruscic G3X
8.5	9324.4	CH2S (g, singlet) + H2 (g) → CH3SH (g)	Δ_rH°(0 K) = -32.76 ± 1.50 kcal/mol	Ruscic W1RO
7.5	9326.5	CH3SH (g) → [CH2S]+ (g) + H2 (g)	Δ_rH°(0 K) = 10.810 ± 0.040 (×1.756) eV	Ruscic W1RO
7.5	9324.2	CH2S (g, singlet) + H2 (g) → CH3SH (g)	Δ_rH°(0 K) = -30.64 ± 1.60 kcal/mol	Ruscic G4
7.4	9325.3	CH2S (g, singlet) + CH3OH (g) → CH3SH (g) + CH2O (g, singlet)	Δ_rH°(0 K) = -11.82 ± 1.6 kcal/mol	Ruscic CBS-n
7.0	9326.3	CH3SH (g) → [CH2S]+ (g) + H2 (g)	Δ_rH°(0 K) = 10.708 ± 0.073 eV	Ruscic G4
6.5	9324.1	CH2S (g, singlet) + H2 (g) → CH3SH (g)	Δ_rH°(0 K) = -30.39 ± 1.72 kcal/mol	Ruscic G3X
4.3	9326.2	CH3SH (g) → [CH2S]+ (g) + H2 (g)	Δ_rH°(0 K) = 10.683 ± 0.093 eV	Ruscic G3X
4.1	9324.3	CH2S (g, singlet) + H2 (g) → CH3SH (g)	Δ_rH°(0 K) = -30.46 ± 2.16 kcal/mol	Ruscic CBS-n
3.8	9326.4	CH3SH (g) → [CH2S]+ (g) + H2 (g)	Δ_rH°(0 K) = 10.671 ± 0.099 eV	Ruscic CBS-n

Top 10 species with enthalpies of formation correlated to the Δ_fH° of [CH2S]+ (g)

Please note: The correlation coefficients are obtained by renormalizing the off-diagonal elements of the covariance matrix by the corresponding variances.
The correlation coefficient is a number from -1 to 1, with 1 representing perfectly correlated species, -1 representing perfectly anti-correlated species, and 0 representing perfectly uncorrelated species.

Correlation Coefficent (%)	Species Name	Formula	Δ_fH°(0 K)	Δ_fH°(298.15 K)	Uncertainty	Units	Relative Molecular Mass	ATcT ID
98.9	Thioformaldehyde	CH2S (g, singlet)	121.3	117.6	± 2.0	kJ/mol	46.0926 ± 0.0061	865-36-1*2
98.9	Thioformaldehyde	CH2S (g)	121.3	117.6	± 2.0	kJ/mol	46.0926 ± 0.0061	865-36-1*0
98.9	Thioformaldehyde	CH2S (g, triplet)	294.9	292.3	± 2.0	kJ/mol	46.0926 ± 0.0061	865-36-1*3
72.5	Thioformaldehyde anion	[CH2S]- (g)	75.8	72.8	± 2.7	kJ/mol	46.0931 ± 0.0061	71928-47-7*0
23.0	Methanethiol	CH3SH (g)	-10.39	-20.66	± 0.46	kJ/mol	48.1085 ± 0.0061	74-93-1*0
22.8	Methanethiol cation	[CH3SH]+ (g)	901.89	891.85	± 0.46	kJ/mol	48.1079 ± 0.0061	53369-41-8*0
20.5	Methanethiol	CH3SH (cr,l)	-46.75	-44.57	± 0.44	kJ/mol	48.1085 ± 0.0061	74-93-1*500
6.1	Sulfuric acid	OS(O)(OH)2 (aq, 30 H2O)		-885.87	± 0.13	kJ/mol	98.0795 ± 0.0061	7664-93-9*820
6.1	Sulfuric acid	OS(O)(OH)2 (aq, 100 H2O)		-887.52	± 0.13	kJ/mol	98.0795 ± 0.0061	7664-93-9*828
6.1	Sulfuric acid	OS(O)(OH)2 (aq, 50 H2O)		-886.66	± 0.13	kJ/mol	98.0795 ± 0.0061	7664-93-9*822

Most Influential reactions involving [CH2S]+ (g)

Please note: The list, which is based on a hat (projection) matrix analysis, is limited to no more than 20 largest influences.

Influence Coefficient	TN ID	Reaction	Measured Quantity	Reference
0.956	9320.1	CH2S (g, singlet) → [CH2S]+ (g)	Δ_rH°(0 K) = 9.376 ± 0.003 eV	Ruscic 1993b
0.080	9326.5	CH3SH (g) → [CH2S]+ (g) + H2 (g)	Δ_rH°(0 K) = 10.810 ± 0.040 (×1.756) eV	Ruscic W1RO
0.074	9326.3	CH3SH (g) → [CH2S]+ (g) + H2 (g)	Δ_rH°(0 K) = 10.708 ± 0.073 eV	Ruscic G4
0.045	9326.2	CH3SH (g) → [CH2S]+ (g) + H2 (g)	Δ_rH°(0 K) = 10.683 ± 0.093 eV	Ruscic G3X
0.040	9326.4	CH3SH (g) → [CH2S]+ (g) + H2 (g)	Δ_rH°(0 K) = 10.671 ± 0.099 eV	Ruscic CBS-n
0.022	9326.1	CH3SH (g) → [CH2S]+ (g) + H2 (g)	Δ_rH°(0 K) = 10.61 ± 0.05 (×2.65) eV	Kutina 1982a
0.021	9320.3	CH2S (g, singlet) → [CH2S]+ (g)	Δ_rH°(0 K) = 9.38 ± 0.02 eV	Solouki 1976, est unc
0.005	9320.2	CH2S (g, singlet) → [CH2S]+ (g)	Δ_rH°(0 K) = 9.338 ± 0.010 (×3.83) eV	Kroto 1972
0.005	9320.8	CH2S (g, singlet) → [CH2S]+ (g)	Δ_rH°(0 K) = 9.390 ± 0.040 eV	Ruscic W1RO
0.003	9320.4	CH2S (g, singlet) → [CH2S]+ (g)	Δ_rH°(0 K) = 9.33 ± 0.05 eV	Guimon 1974, est unc
0.001	9320.6	CH2S (g, singlet) → [CH2S]+ (g)	Δ_rH°(0 K) = 9.379 ± 0.073 eV	Ruscic G4
0.001	9320.5	CH2S (g, singlet) → [CH2S]+ (g)	Δ_rH°(0 K) = 9.365 ± 0.093 eV	Ruscic G3X
0.000	9320.7	CH2S (g, singlet) → [CH2S]+ (g)	Δ_rH°(0 K) = 9.350 ± 0.099 eV	Ruscic CBS-n

References

1		B. Ruscic, R. E. Pinzon, M. L. Morton, G. von Laszewski, S. Bittner, S. G. Nijsure, K. A. Amin, M. Minkoff, and A. F. Wagner, Introduction to Active Thermochemical Tables: Several "Key" Enthalpies of Formation Revisited. J. Phys. Chem. A 108, 9979-9997 (2004) [DOI: 10.1021/jp047912y]
2		B. Ruscic, R. E. Pinzon, G. von Laszewski, D. Kodeboyina, A. Burcat, D. Leahy, D. Montoya, and A. F. Wagner, Active Thermochemical Tables: Thermochemistry for the 21^st Century. J. Phys. Conf. Ser. 16, 561-570 (2005) [DOI: 10.1088/1742-6596/16/1/078]
3		B. Ruscic and D. H. Bross, Active Thermochemical Tables (ATcT) values based on ver. 1.148 of the Thermochemical Network (2023); available at ATcT.anl.gov
4		T. L. Nguyen, J. Peeters, J.-F. Müller, A. Perera, D. H. Bross, B. Ruscic, and J. F. Stanton, Methanediol from Cloud-Processed Formaldehyde is Only a Minor Source of Atmospheric Formic Acid Natl. Acad. Sci. 120, e2304650120/1-8 (2023) [DOI: 10.1073/pnas.2304650120]
5		B. Ruscic, Uncertainty Quantification in Thermochemistry, Benchmarking Electronic Structure Computations, and Active Thermochemical Tables. Int. J. Quantum Chem. 114, 1097-1101 (2014) [DOI: 10.1002/qua.24605]
6		B. Ruscic and D. H. Bross, Thermochemistry Computer Aided Chem. Eng. 45, 3-114 (2019) [DOI: 10.1016/B978-0-444-64087-1.00001-2]

Formula

The aggregate state is given in parentheses following the formula, such as: g - gas-phase, cr - crystal, l - liquid, etc.

Uncertainties

The listed uncertainties correspond to estimated 95% confidence limits, as customary in thermochemistry (see, for example, Ruscic [5] and Ruscic and Bross[6]).
Note that an uncertainty of ± 0.000 kJ/mol indicates that the estimated uncertainty is < ± 0.000₅ kJ/mol.

Website Functionality Credits

The reorganization of the website was developed and implemented by David H. Bross (ANL).
The find function is based on the complete Species Dictionary entries for the appropriate version of the ATcT TN.
The molecule images are rendered by Indigo-depict.
The XYZ renderings are based on Jmol: an open-source Java viewer for chemical structures in 3D. http://www.jmol.org/.

Acknowledgement

This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Contract No. DE-AC02-06CH11357.