HCNH+

HCNH⁺, also known as protonated hydrogen cyanide, is a molecular ion of astrophysical interest.

Structure

The ground state structure of HCNH⁺ is a simple linear molecule. In addition, there are multiple higher-energy isomers such as CNH+
2, H₂CN⁺, cis-HCNH⁺, and trans-HCNH⁺. ^[1]

Laboratory studies

As a relatively simple molecular ion, HCNH⁺ has been extensively studied in the laboratory. The very first spectrum taken at any wavelength focused on the ν₂ (C−H stretch) ro-vibrational band in the infrared. ^[2] Soon afterward, the same authors reported on their investigation of the ν₁ (N−H stretch) band. ^[3] Following these initial studies, several groups published manuscripts on the various ro-vibrational spectra of HCNH⁺, including studies of the ν₃ band (C≡N stretch) ,^[4] the ν₄ band (H−C≡N bend) ,^[5] and the ν₅ band (H−N≡C bend) .^[6]

While all of these studies focused on ro-vibrational spectra in the infrared, it was not until 1998 that technology advanced far enough for an investigation of the pure rotational spectrum of HCNH⁺ in the microwave region to take place. At that time, microwave spectra for HCNH⁺ and its isotopomers HCND⁺ and DCND⁺ were published.^[7] Recently, the pure rotational spectrum of HCNH⁺ was measured again in order to more precisely determine the molecular rotational constants B and D.^[8]

Spectrum

As mentioned above, the most recent laboratory measurement of the pure rotational spectrum of the ground state of HCNH⁺ was performed in 2006.^[8] This study determined the most precise values of the molecular constants to date. Using these constants in conjunction with the program PGOPHER, one can generate the predicted rotational spectrum for the ground state of HCNH⁺ at a temperature of 30 K, as shown below. Being a linear molecule, HCNH⁺ follows the basic rotational selection rule of ΔJ = ±1.

Formation and destruction

According to the database at astrochemistry.net, the most advanced chemical models of HCNH⁺ include 71 total formation reactions and 21 total destruction reactions. Of these, however, only a handful dominate the overall formation and destruction. In the case of formation, the 7 dominant reactions are:

H+
3 + HCN → HCNH⁺ + H₂

H+
3 + HNC → HCNH⁺ + H₂

HCO⁺ + HCN → HCNH⁺ + CO

HCO⁺ + HNC → HCNH⁺ + CO

H₃O⁺ + HCN → HCNH⁺ + H₂O

H₃O⁺ + HNC → HCNH⁺ + H₂O

C⁺ + NH₃ → HCNH⁺ + H

Using rate coefficients from astrochemistry.net and the UMIST Database for Astrochemistry in conjunction with model interstellar abundances ^[9] one can calculate the relative importance of these 7 reactions as shown in the table below.

Reactant 1	Reactant 2	Product 1	Product 2	Relative importance (%)
H+ 3	HCN	HCNH^+	H2	14
H+ 3	HNC	HCNH^+	H2	25
HCO^+	HCN	HCNH^+	CO	10
HCO^+	HNC	HCNH^+	CO	18
H3O^+	HCN	HCNH^+	H2O	2
H3O^+	HNC	HCNH^+	H2O	4
C^+	NH3	HCNH^+	H	27

Being an ion, HCNH⁺ is predominantly destroyed by the electron recombination reactions:

e⁻ + HCNH⁺ → HCN + H

e⁻ + HCNH⁺ → HNC + H

e⁻ + HCNH⁺ → CN + H + H

Using the same sources as above, the relative importance of these destruction reactions are calculated and shown in the table below. Also shown in the table is the ion-neutral reaction HCNH⁺ + H₂CO, in order to demonstrate just how dominant electron recombination is.

Reactant 1	Reactant 2	Product 1	Product 2	Relative importance (%)
e^−	HCNH^+	HCN	H	33.5
e^−	HCNH^+	HNC	H	33.5
e^−	HCNH^+	CN	H + H	33
H2CO	HCNH^+	HCN	H3CO^+	0.08
H2CO	HCNH^+	HNC	H3CO^+	0.08

Astronomical detections

Initial interstellar detection

HCNH⁺ was first detected in interstellar space in 1986 toward the dense cloud Sgr B2 using the NRAO 12 m dish and the Texas Millimeter Wave Observatory.^[10] These observations utilized the J = 1–0, 2–1, and 3–2 pure rotational transitions at 74, 148, and 222 GHz, respectively.

Subsequent interstellar detections

Since the initial detection, HCNH⁺ has also been observed in TMC-1^{[11] [12]} as well as DR 21(OH)^[11] .^[13] The initial detection toward Sgr B2 has also been confirmed.^[11][14] All 3 of these sources are dense molecular clouds, and to date HCNH⁺ has not been detected in diffuse interstellar material.

Solar System bodies

While not directly detected via spectroscopy, the existence of HCNH⁺ has in fact been inferred in the atmosphere of Saturn's largest moon, Titan.^[15] This was done using the Ion and Neutral Mass Spectrometer (INMS) instrument aboard the Cassini space probe. Models of Titan's atmosphere had predicted that HCNH⁺ would be the dominant ion present, and a strong peak in the mass spectrum at Z/M=28 seems to support this theory.

In 1997, observations were made of the long-period comet Hale–Bopp in an attempt to find HCNH⁺, ^[16] but it was not detected. However, the upper limit derived from these observations, along with the detections of HCN, HNC, and CN, is important in understanding the chemistry associated with comets.

References

1. Allen, T. L., Goddard, J. D., & Schaefer, H. F. III (1980). "A possible role for triplet H₂CN⁺ isomers in the formation of HCN and HNC in interstellar clouds". Journal of Chemical Physics. 73 (7): 3255–3263. Bibcode:1980JChPh..73.3255A. doi:10.1063/1.440520.
2. Altman, R. S., Crofton, M. W., & Oka, T. (1984). "Observation of the infrared ν₂ band (CH stretch) of protonated hydrogen cyanide, HCNH⁺". Journal of Chemical Physics. 80 (8): 3911–3912. Bibcode:1984JChPh..80.3911A. doi:10.1063/1.447173.
3. Altman, R. S., Crofton, M. W., & Oka, T. (1984). "High resolution infrared spectroscopy of the ν₁ (NH stretch) and ν₂ (CH stretch) bands of HCNH⁺". Journal of Chemical Physics. 81 (10): 4255–4258. Bibcode:1984JChPh..81.4255A. doi:10.1063/1.447433.
4. Kajita, M., Kawaguchi, K., & Hirota, E. (1988). "Diode laser spectroscopy of the ν₃ (CN stretch) band of HCNH⁺". Journal of Molecular Spectroscopy. 127 (1): 275–276. Bibcode:1988JMoSp.127..275K. doi:10.1016/0022-2852(88)90026-4.
5. Tanaka, K., Kawaguchi, K., & Hirota, E. (1986). "Diode laser spectroscopy of the ν₄ (HCN bend) band of HCNH⁺". Journal of Molecular Spectroscopy. 117 (2): 408–415. Bibcode:1986JMoSp.117..408T. doi:10.1016/0022-2852(86)90164-5.
6. Ho, W.-C., Blom, C. E., Liu, D.-J., & Oka, T. (1987). "The infrared ν₅ band (HNC bend) of protonated hydrogen cyanide, HCNH⁺". Journal of Molecular Spectroscopy. 123 (1): 251–253. Bibcode:1987JMoSp.123..251H. doi:10.1016/0022-2852(87)90275-X.
7. Araki, M., Ozeki, H., & Saito, S. (1998). "Laboratory Measurement of the Pure Rotational Transitions of HCNH⁺ and Its Isotopic Species". Astrophysical Journal Letters. 496 (1): L53. arXiv:astro-ph/9801241. Bibcode:1998ApJ...496L..53A. doi:10.1086/311245.
8. Amano, T., Hashimoto, K., & Hirao, T. (2006). "Submillimeter-wave spectroscopy of HCNH⁺ and CH₃CNH⁺". Journal of Molecular Structure. 795 (1–3): 190–193. Bibcode:2006JMoSt.795..190A. doi:10.1016/j.molstruc.2006.02.035.
9. Millar, T. J., Farquhar, P. R. A., & Willacy, K. (1997). "The UMIST Database for Astrochemistry 1995". Astronomy & Astrophysics Supplement Series. 121 (1): 139–185. Bibcode:1997A&AS..121..139M. doi:10.1051/aas:1997118.
10. Ziurys, L. M.; Turner, B. E. (1986). "HCNH⁺: A New Interstellar Molecular Ion" (PDF). The Astrophysical Journal Letters. 302: L31–L36. Bibcode:1986ApJ...302L..31Z. doi:10.1086/184631.
11. Schilke, P., Walmsley, C. M., Millar, T. J., & Henkel, C. (1991). "Protonated HCN in molecular clouds". Astronomy & Astrophysics. 247: 487–496. Bibcode:1991A&A...247..487S.
12. Ziurys, L. M., Apponi, A. J., & Yoder, J. T. (1992). "Detection of the Quadrupole Hyperfine Structure in HCNH⁺". The Astrophysical Journal Letters. 397: L123–L126. Bibcode:1992ApJ...397L.123Z. doi:10.1086/186560.
13. Hezareh, T., Houde, M., McCoey, C., Vastel, C., & Peng, R. (2008). "Simultaneous Determination of the Cosmic Ray Ionization Rate and Fractional Ionization in DR 21(OH)". The Astrophysical Journal. 684 (2): 1221–1227. arXiv:0805.4018. Bibcode:2008ApJ...684.1221H. doi:10.1086/590365.
14. Nummelin, A., Bergman, P., Hjalmarson, Å., Friberg, P., Irvine, W. M., Millar, T. J., Ohishi, M., & Saito, S. (2000). "A Three-Position Spectral Line Survey of Sagittarius B2 between 218 and 263 GHZ. II. Data Analysis". The Astrophysical Journal Supplement Series. 128 (1): 213–243. Bibcode:2000ApJS..128..213N. doi:10.1086/313376.
15. Cravens, T. E., Robertson, I. P., Waite, J. H., Yelle, R. V., Kasprzak, W. T., Keller, C. N., Ledvina, S. A., Niemann, H. B., Luhmann, J. G., McNutt, R. L., Ip, W.-H., De La Haye, V., Mueller-Wodarg, I., Wahlund, J.-E., Anicich, V. G., & Vuitton, V. (2006). "Composition of Titan's atmosphere". Geophysical Research Letters. 33 (7): L07105. Bibcode:2006GeoRL..3307105C. doi:10.1029/2005GL025575.
16. Ziurys, L. M., Savage, C., Brewster, M. A., Apponi, A. J., Pesch, T. C., & Wyckoff, S. (1999). "Cyanide Chemistry in Comet Hale-Bopp (C/1995 O1)". The Astrophysical Journal Letters. 527 (1): L67–L71. Bibcode:1999ApJ...527L..67Z. doi:10.1086/312388.