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See detailOrtho-to-para abundance ratios of NH2in 26 comets: implications for the real meaning of OPRs
Shinnaka, Yoshiharu; Kawakita, Hideyo; Jehin, Emmanuel ULg et al

in Monthly Notices of the Royal Astronomical Society (2016), 462

Abundance ratios of nuclear-spin isomers for cometary molecules having identical protons, such as water and ammonia, have been measured and discussed from the viewpoint that they are primordial characters ... [more ▼]

Abundance ratios of nuclear-spin isomers for cometary molecules having identical protons, such as water and ammonia, have been measured and discussed from the viewpoint that they are primordial characters in comet. In the case of ammonia, its ortho-to-para abundance ratio (OPR) is usually estimated from OPRs of NH2 because of difficulty in measuring OPR of ammonia directly. We report our survey for OPRs of NH2 in 26 comets. A weighted mean of ammonia OPRs for the comets is 1.12 ± 0.01 and no significant difference is found between the Oort Cloud comets and the Jupiter-family comets. These values correspond to ∼30 K as nuclear-spin temperatures. The OPRs of ammonia in comets probably reflect the physicochemical conditions in coma, rather than the conditions for the molecular formation or condensation in the pre-solar molecular cloud/the solar nebula, based on comparison of OPRs (and nuclear-spin temperatures) of ammonia with those of water, 14N/15N ratios in ammonia, and D/H ratios in water. The OPRs could be reset to a nuclear-spin weights ratio in solid phase and modified by interactions with protonated ions like H3O+, water clusters (H2O)n, ice grains, and paramagnetic impurities (such as O2 molecules and grains) in the inner coma gas. Relationship between the OPRs of ammonia and water is a clue to understanding the real meaning of the OPRs. [less ▲]

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See detailNitrogen isotopic ratios of NH 2 in comets: implication for 15 N-fractionation in cometary ammonia
Shinnaka, Yoshiharu; Kawakita, Hideyo; Jehin, Emmanuel ULg et al

in Monthly Notices of the Royal Astronomical Society (2016), 462

The isotopic ratios are diagnostics for the physico-chemical conditions governing molecular formation. In comets, 14N/15N ratios have been measured from HCN in three comets and from CN in more than 20 ... [more ▼]

The isotopic ratios are diagnostics for the physico-chemical conditions governing molecular formation. In comets, 14N/15N ratios have been measured from HCN in three comets and from CN in more than 20 comets. Those ratios are enriched in 15N compared to the Sun by a factor of ∼3, have a small diversity and do not depend on the dynamical type of the comets. The origin of this high 15N-fractionation is still in debate because CN probably comes not only from HCN, but also from other materials (such as polymers or organic dusts) in the coma. Consequently, an interpretation of the isotopic ratios in cometary CN is quite complicated due to the multiple possible parents of CN. In contrast with CN, the isotopic ratios of nitrogen in NH3 give us a much clearer interpretation than in CN because NH3 is directly incorporated in the nuclear ices. To estimate the 14N/15N ratios in NH3, 14N/15N ratios have been determined from high-resolution spectra of NH2 in the optical wavelength region. NH2 is indeed a dominant photodissociation product of NH3. Those ratios were also found to be enriched in 15N compared to the Sun by a factor of ∼3. In this paper, we present 14N/15N ratios in NH2 for an additional sample of 16 comets. Our sample includes short-period comets as well as long-period comets. We found that the 14N/15N ratios in cometary NH2 also show a small dispersion and do not depend on the dynamical origin of the comets. [less ▲]

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See detailSurvey for Ortho-to-Para Abundance Ratios (OPRs) of NH2 in Comets: Revisit to the Meaning of OPRs of Cometary Volatiles
Kawakita, Hideyo; Shinnaka, Yoshiharu; Jehin, Emmanuel ULg et al

in Bulletin of the American Astronomical Society (2016, October 01), 48

Since molecules having identical protons can be classified into nuclear-spin isomers (e.g., ortho-H[SUB]2[/SUB]O and para-H[SUB]2[/SUB]O for water) and their inter-conversions by radiative and non ... [more ▼]

Since molecules having identical protons can be classified into nuclear-spin isomers (e.g., ortho-H[SUB]2[/SUB]O and para-H[SUB]2[/SUB]O for water) and their inter-conversions by radiative and non-destructive collisional processes are believed to be very slow, the ortho-to-para abundance ratios (OPRs) of cometary volatiles such as H[SUB]2[/SUB]O, NH[SUB]3[/SUB] and CH[SUB]4[/SUB] in coma have been considered as primordial characters of cometary molecules [1]. Those ratios are usually interpreted as nuclear-spin temperatures although the real meaning of OPRs is in strong debate. Recent progress in laboratory studies about nuclear-spin conversion in gas- and solid-phases [2,3] revealed short-time nuclear-spin conversions for water, and we have to reconsider the interpretation for observed OPRs of cometary volatiles. We have already performed the survey for OPRs of NH[SUB]2[/SUB] in more than 20 comets by large aperture telescopes with high-resolution spectrographs (UVES/VLT, HDS/Subaru, etc.) in the optical wavelength region [4]. The observed OPRs of ammonia estimated from OPRs of NH[SUB]2[/SUB], cluster around ~1.1 (cf. 1.0 as a high-temperature limit), indicative of ~30 K as nuclear-spin temperatures. We present our latest results for OPRs of cometary NH[SUB]2[/SUB] and discuss about the real meaning of OPRs of cometary ammonia, in relation to OPRs of water in cometary coma. Chemical processes in the inner coma may play an important role to achieve un-equilibrated OPRs of cometary volatiles in coma.This work was financially supported by MEXT Supported Program for the Strategic Research Foundation at Private Universities, 2014–2018 (No. S1411028) (HK) and by Graint-in-Aid for JSPS Fellows, 15J10864 (YS).References:[1] Mumma & Charnley, 2011, Annu. Rev. Astro. Astrophys. 49, 471.[2] Hama & Watanabe, 2013, Chem. Rev. 113, 8783.[3] Hama et al., 2008, Science 351, 6268.[4] Shinnaka et al., 2011, ApJ 729, 81. [less ▲]

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See detailNitrogen Isotopic Ratios in Cometary NH2: Implication for 15N-fractionation in Ammonia
Shinnaka, Yoshiharu; Kawakita, Hideyo; Jehin, Emmanuel ULg et al

in Bulletin of the American Astronomical Society (2015, November 01), 47

Isotopic ratios in cometary molecules are diagnostic for the physico-chemical conditions where molecules formed and are processed, from the interstellar medium to the solar nebula. Usually temperatures at ... [more ▼]

Isotopic ratios in cometary molecules are diagnostic for the physico-chemical conditions where molecules formed and are processed, from the interstellar medium to the solar nebula. Usually temperatures at the molecular formation control the fractionation of the heavier element in molecular species, e.g., D-fractionation in water.In cometary volatiles, the [SUP]14[/SUP]N/[SUP]15[/SUP]N ratios in CN have been well observed (Manfroid et al. 2009, A&A, 503, 613, and reference therein) and is consistent with the ratio in HCN (a most probable parent of CN) measured in few comets (Bockelée-Morvan et al. 2008, ApJ, 679, L49). Those ratios are enriched compared to the proto-solar value by a factor of ~3. In contrast to those Nitriles, there are only few reports on [SUP]14[/SUP]N/[SUP]15[/SUP]N ratios in Ammonia (as Amine) (Rousselot et al. 2014, ApJ, 780, L17; Shinnaka et al. 2014, ApJ, 782, L16). Ammonia (NH[SUB]3[/SUB]) is usually the most abundant and HCN is the second most abundant N-bearing volatiles in cometary ice. Especially, recent observations of [SUP]15[/SUP]NH[SUB]2[/SUB] revealed the [SUP]14[/SUP]N/[SUP]15[/SUP]N ratios in NH[SUB]3[/SUB] are comparable to those of CN. However, from the viewpoint of theoretical work, the enrichment of [SUP]15[/SUP]N in cometary NH[SUB]3[/SUB] cannot be reproduced by current chemical network models. Information about the diversity of the [SUP]14[/SUP]N/[SUP]15[/SUP]N ratios in NH[SUB]3[/SUB] of individual comets is needed to understand the formation mechanisms/environments of NH[SUB]3[/SUB] in the early solar system.To clarify the diversity of the [SUP]14[/SUP]N/[SUP]15[/SUP]N ratios in cometary NH[SUB]3[/SUB], we determine the [SUP]14[/SUP]N/[SUP]15[/SUP]N ratios in NH[SUB]3[/SUB] for more than ten comets individually which include not only Oort cloud comets but also short period comets by using the high-resolution optical spectra of NH[SUB]2[/SUB]. These spectra were obtained with both the UVES mounted on the VLT in Chile and the HDS on the Subaru Telescope in Hawaii.The derived [SUP]14[/SUP]N/[SUP]15[/SUP]N ratios in NH[SUB]3[/SUB] for more than ten comets show high [SUP]15[/SUP]N-enrichment compared with the elemental abundances of nitrogen in the Sun by about factor of ~3 and has no large diversity depending on these dynamical properties. We discuss about the origin of the formation conditions of cometary NH[SUB]3[/SUB] and its physico-chemical evolution in the solar nebula based on our and other results.This work was supported by JSPS, 15J10864 (Y. Shinnaka). [less ▲]

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See detailHigh-Dispersion Spectroscopic Observations of Comet C/2012 S1 (ISON) with the Subaru Telescope
Shinnaka, Yoshiharu; Kawakita, Hideyo; Nagashima, Masayoshi et al

in Bulletin of the American Astronomical Society (2014, November 01), 46

Comet C/2012 S1 (ISON) was one of the Oort cloud comets and dynamically new. This comet was broken at its perihelion passage on UT 2013 November 28.1 (at Rh ~ 17 solar radius). We observed the comet C ... [more ▼]

Comet C/2012 S1 (ISON) was one of the Oort cloud comets and dynamically new. This comet was broken at its perihelion passage on UT 2013 November 28.1 (at Rh ~ 17 solar radius). We observed the comet C/2012 S1 (ISON) on UT 2013 November 15 with the High Dispersion Spectrograph (HDS) mounted on the Subaru Telescope atop Mauna Kea, Hawaii. Its heliocentric and geocentric distances were 0.601 and 0.898 AU, respectively. We selected the slit size of 0”.5 x 9”.0 on the sky to achieve the spectral resolution of R = 72,000 from 550 to 830 nm. The total exposure time of comet C/2012 S1 (ISON) was 1200 seconds. We detected many emission lines caused from radicals (e.g., CN, C2, NH2), ions (H2O+), atoms ([OI] and Na I) and also many unidentified lines in the spectra. We report the (1) the ortho-to-para abundance ratios (OPRs) of water and ammonia estimated from the high-dispersion spectra of H2O+ and NH2, (2) the green-to-red line ratio of forbidden oxygen emissions, (3) the isotopic ratios of C2 (the carbon isotopic ratio from Swan band) and CN (the carbon and nitrogen isotopic ratios from red band), (4) the sodium-to-continuum ratio of comet C/2012 S1 (ISON). </PRE></BODY></HTML> [less ▲]

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See detailOrtho-to-para Abundance Ratio (OPR) of Ammonia in 15 Comets: OPRs of Ammonia Versus 14N/15N Ratios in CN
Shinnaka, Yoshiharu; Kawakita, Hideyo; Kobayashi, Hitomi et al

in Astrophysical Journal (2011), 729

The ortho-to-para abundance ratio (OPR) of cometary molecules is considered to be one of the primordial characteristics of cometary ices. We present OPRs of ammonia (NH[SUB]3[/SUB]) in 15 comets based on ... [more ▼]

The ortho-to-para abundance ratio (OPR) of cometary molecules is considered to be one of the primordial characteristics of cometary ices. We present OPRs of ammonia (NH[SUB]3[/SUB]) in 15 comets based on optical high-dispersion spectroscopic observations of NH[SUB]2[/SUB], which is a photodissociation product of ammonia in the gaseous coma. The observations were mainly carried out with the VLT/UVES. The OPR of ammonia is estimated from the OPR of NH[SUB]2[/SUB] based on the observations of the NH[SUB]2[/SUB] (0, 9, 0) vibronic band. The absorption lines by the telluric atmosphere are corrected and the cometary C[SUB]2[/SUB] emission lines blended with NH[SUB]2[/SUB] lines are removed in our analysis. The ammonia OPRs show a cluster between 1.1 and 1.2 (this corresponds to a nuclear spin temperature of ~30 K) for all comets in our sample except for 73P/Schwassmann-Wachmann 3 (73P/SW3). Comet 73P/SW3 (both B- and C-fragments) shows the OPR of ammonia consistent with nuclear spin statistical weight ratio (1.0) that indicates a high-temperature limit as nuclear spin temperature. We compared the ammonia OPRs with other properties ([SUP]14[/SUP]N/[SUP]15[/SUP]N ratios in CN, D/H ratios of water, and mixing ratios of volatiles). Comet 73P/SW3 is clearly different from the other comets in the plot of ammonia OPRs versus [SUP]14[/SUP]N/[SUP]15[/SUP]N ratios in CN. The ammonia OPRs of 1.0 and lower [SUP]15[/SUP]N-fractionation of CN in comet 73P/SW3 imply that icy materials in this comet formed under warmer conditions than other comets. Comets may be classified into two groups in the plot of ammonia OPRs against [SUP]14[/SUP]N/[SUP]15[/SUP]N ratios in CN. [less ▲]

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See detailOPRs of Ammonia versus 14N/15N Ratios in CN in 15 Comets
Shinnaka, Yoshiharu; Kawakita, H.; Kobayashi, H. et al

in Bulletin of the American Astronomical Society (2010, October 01), 42

The solar system was formed from interstellar matter 4.6 Gyrs ago and comets are considered as remnants of icy planetesimals formed in the early solar system. One of interesting primordial characters of ... [more ▼]

The solar system was formed from interstellar matter 4.6 Gyrs ago and comets are considered as remnants of icy planetesimals formed in the early solar system. One of interesting primordial characters of cometary ice is an ortho-to-para abundance ratio (OPR) of molecules such as H2O, NH3, etc. The OPR probably indicates the molecular formation temperatures in the solar nebula or in the pre-solar molecular cloud. We determined the OPRs of ammonia by using the high dispersion optical spectra of NH2 in 15 comets: C/1995 O1 (Hale-Bopp), C/1999 S4 (LINEAR), C/2001 A2 (LINEAR), C/2000 WM1 (LINEAR), 153P/Ikeya-Zhang, C/2002 V1 (NEAT), C/2002 X5 (Kudo-Fujikawa), C/2002 Y1 (Juels-Holvorcem), C/2001 Q4 (NEAT), C/2002 T7 (LINEAR), C/2003 K4 (LINEAR), 8P/Tuttle, 88P/Howell, 9P/Tempel 1, and 73P-B and -C/Schwassmann-Wachmann 3. The observations were mainly carried out by the Ultraviolet and Visual Echelle Spectrograph (UVES) mounted on the Very Large Telescope (VLT) in Chile. Other telescopes/instruments were also used in some cases. The OPRs of ammonia are determined from OPRs of NH2 (0,9,0) ro-vibronic band around 600 nm. Although absorption lines (by the telluric atmosphere) and cometary C2 emission lines blended affected to NH2 emission lines in this region, we removed them in our analysis. The determined OPRs of ammonia clustered around 30K but not in the cases of 73P-B and -C. This situation is very similar to that of 14N/15N ratios in CN (i.e., 73P-B and -C are quite peculiar relative to other comets). We discuss about the relationship between the OPRs of ammonia and 14N/15N ratios in CN in these 15 comets. Our results indicate the formation of materials at relatively higher temperatures for 73P-B and -C than other comets. [less ▲]

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See detailRevisit to Nuclear Spin Temperature of Ammonia in Comets
Shinnaka, Yoshiharu; Jehin, Emmanuel ULg; Manfroid, Jean ULg et al

in Bulletin of the American Astronomical Society (2009, September 01), 41

Comets had formed from dust and icy materials in the solar nebula 4.6 Gyrs ago. The cometary materials are considered as the most pristine in the solar system and both dust grains and icy materials in ... [more ▼]

Comets had formed from dust and icy materials in the solar nebula 4.6 Gyrs ago. The cometary materials are considered as the most pristine in the solar system and both dust grains and icy materials in comets have been used to investigate the formation conditions of the solar system. One of interesting primordial characters is a nuclear spin temperature (related to an ortho-to-para ratio; OPR) of cometary molecules such as H2O, NH3, etc. The nuclear spin temperatures probably reflect the molecular formation temperatures in the solar nebula (or in the presolar molecular cloud). In this work, we analyzed high dispersion optical spectra of C/2001 Q4 (NEAT), C/2000 WM1 (LINEAR), 88P/Howell, fragments B and C of 73P/Schwassmann-Wachmann 3 and 8P/Tuttle. Our observations were performed by the Ultraviolet and Visual Echelle Spectrograph (UVES) mounted on the Very Large Telescope (VLT) in Chile and the High Dispersion Spectrograph (HDS) mounted on the Subaru telescope in Hawaii. We determined nuclear spin temperatures of NH3 in five comets based on optical spectra of NH2. The nuclear spin temperatures of NH3 can be obtained from OPRs of NH2. We used the (0,9,0) ro-vibronic band at 610nm in this work. Absorption lines (by the telluric atmosphere) and cometary C2 emission lines blended with NH2 emission lines were also taken into account in our analysis. These lines have never been considered in previous studies. The origin of icy materials in the five comets will be discussed based on these results. [less ▲]

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