L29

The Astrophysical Journal, 666:L29L32, 2007 September 1

2007. The American Astronomical Society. All rights reserved. Printed in U.S.A.
IDENTIFICATION OF PHOSPHORUS MONOXIDE (X
2
P
r
) IN VY CANIS MAJORIS:
DETECTION OF THE FIRST PiO BOND IN SPACE
E. D. Tenenbaum,
1,2
N. J. Woolf,
1
and L. M. Ziurys
1,2,3
Received 2007 June 11; accepted 2007 July 5; published 2007 August 17
ABSTRACT
A new interstellar molecule, PO (X
2
P
r
), has been detected toward the envelope of the oxygen-rich supergiant
star VY Canis Majoris (VY CMa) using the Submillimeter Telescope of the Arizona Radio Observatory. The
and rotational transitions of PO at 240 and 284 GHz were observed, each of which J p 5.5 r 4.5 J p 6.5 r 5.5
consisted of well-dened lambda-doublets. The line proles are roughly parabolic in shape, analogous to PN,
and suggest that this species arises from the spherical wind in VY CMa, as opposed to the collimated blue- and
redshifted outows. Comparison of line intensities indicates that PO arises from a conned source roughly 1 in
extent, with a column density of N
tot
2.8 # 10
15
cm
2
, which corresponds to a fractional abundance of f
, relative to H
2
. Consequently, PO and PN have similar concentrations in VY CMa, a result not predicted
8
9 #10
by either LTE or kinetic models of circumstellar chemistry. These phosphorus compounds may arise from shock-
induced reactions in this active envelope. Phosphorus monoxide is the rst interstellar molecule detected that
contains a PiO bond, a moiety essential in biochemical compounds. It is also the rst new species to be identied
in an oxygen-rich, as opposed to a carbon-rich, circumstellar envelope.
Subject headings: astrobiology astrochemistry circumstellar matter ISM: molecules
radio lines: stars stars: individual (VY Canis Majoris)
1. INTRODUCTION
In terms of mass, phosphorus is the fth most important
biogenic element after carbon, hydrogen, oxygen, and nitrogen
(Pasek & Lauretta 2005). It plays a central role in biochemistry,
particularly when bonded to oxygen in phosphate esters. The
PiO bond is in fact a fundamental unit in DNA, RNA, and
ATP, and thus phosphorus is relevant to both replication and
metabolism in living systems (Macia et al. 1997).
Phosphorus is a relatively abundant element cosmically, with
P/H 3 # 10
7
(Grevesse & Sauval 1998). Therefore, one
might expect that it should play a role in interstellar chemistry.
Yet, to date, only one phosphorus-bearing molecule has been
identied in molecular clouds: PN (Ziurys 1987; Turner &
Bally 1987). In circumstellar gas, PN and the free radical CP
have been observed, but only in one source, the carbon-rich
envelope of IRC 10216 (Guelin et al. 1990, 2000; Cernicharo
et al. 2000; Milam et al. 2007). Very recently, however, HCP
has been identied in this object (Agundez et al. 2007) as well
as in the carbon-rich protoplanetary nebula CRL 2688 (Milam
et al. 2007). Furthermore, PN has now been observed in CRL
2688 and, surprisingly, toward the oxygen-rich shell of the
supergiant star VY CMa (Milam et al. 2007; Ziurys et al. 2007).
Thus, synthesis of phosphorus-containing molecules may our-
ish in circumstellar gas, as has been predicted by thermody-
namic chemical models (Agundez et al. 2007; Tsuji 1973).
In this Letter we present the detection of phosphorus monoxide
in the circumstellar gas of VY Canis Majoris (VY CMa), an
oxygen-rich star not normally considered a source of new mol-
ecules. VYCMa, which lies at a distance of 1.5 kpc, is considered
to be a M5-type supergiant, with a mass of 25 M
,
, an effective
temperature near 3000 K, and a mass-loss rate of (24) #10
4
M
,
yr
1
(Humphreys et al. 2005; Smith et al. 2001; Monnier
1
Department of Astronomy, Steward Observatory, Laplace Center for Astro-
biology, University of Arizona, 933 North Cherry Avenue, Tucson, AZ 85721;
emilyt@as.arizona.edu, nwoolf@as.arizona.edu, lziurys@as.arizona.edu.
2
Department of Chemistry, University of Arizona, Tucson, AZ 85721.
3
Arizona Radio Observatory, University of Arizona, Tucson, AZ 85721.
et al. 2000). The lambda-doublets of the and J p 6.5 r 5.5
rotational transitions at 1 mm were measured J p 5.5 r 4.5
toward this evolved star using the Submillimeter Telescope
(SMT) of the Arizona Radio Observatory (ARO). Here we de-
scribe our results and discuss their implications for phosphorus
chemistry in oxygen-rich circumstellar shells.
2. OBSERVATIONS
The measurements were conducted at the AROs 10 m SMT
located at Mount Graham, Arizona. Observing frequencies and
beam sizes are given in Table 1.
Data collection was carried out during a series of runs from
2007 April to June, using a dual-channel receiver featuring
Atacama Large Millimeter Array (ALMA) Band 6 sideband-
separating mixers (see Lauria et al. 2006). ALMA Band 6
covers the frequency range 211275 GHz. The back end used
was a 2048 channel lter bank with 1 MHz resolution, con-
gured in parallel mode (2 # 1024 channels) for the two
receiver channels. Observations at 240 and 284 GHz were con-
ducted in the lower and upper sidebands, respectively, with
typical rejection of 20 dB for the image sideband. The tem-
perature scale is given in terms of ; the radiation temperature

T
A
is then dened as , with for the

T T p T /h h p 0.770.78
R R A b b
SMT at 1.3 mm.
Data were taken in beam-switching mode with a 2 sub-
reector throw toward the position a p 7
h
20
m
54.7
s
, d p
254012 (B1950.0). Local oscillator shifts were done for
each line to eliminate the possibility of image contamination.
Pointing and focusing were carried out using observations of
Saturn and Venus.
3. RESULTS
Two rotational transitions of PO were observed toward VY
CMa: the at 239.9240.2 GHz and the J p 5.5 r 4.5 J p
at 283.6283.8 GHz. PO has a
2
P
r
ground electronic 6.5 r 5.5
state; therefore, each rotational transition is split into two com-
ponents because of lambda-doubling interactions. In addition,
L30 TENENBAUM, WOOLF, & ZIURYS Vol. 666
TABLE 1
Line Parameters of PO ( ) in VY CMa
2
X P
r
Transition
Frequency
a
(MHz)
b
T
A
(mK)
b
DV
1/2
(km s
1
)
V
LSR
b
(km s
1
)
: J p 5.5 r 4.5
e: . . . . . . F p 6 r 5 239,949.0 7 1 58 5 21 6
e: . . . . . . F p 5 r 4 239,958.1
f: . . . . . . F p 6 r 5 240,141.1 7 1 67 5 29 6
f: . . . . . . F p 5 r 4 240,152.5
: J p 6.5 r 5.5
e: . . . . . . F p 7 r 6 283,586.8 13 2 55 5 25 4
e: . . . . . . F p 6 r 5 283,593.2
f: . . . . . . F p 7 r 6 283,777.6 12 2 51 5 25 5
f: . . . . . . F p 6 r 5 283,785.4
a
Beam sizes at 240 and 284 GHz are 31 and 26, respectively.
b
Line parameters are measured for each lambda-doubling component,
labeled e and f; each component consists of two blended hyperne lines,
indicated by quantum number F.
Fig. 1.Spectra of PO (X
2
P
r
) observed toward the circumstellar shell of
VY CMa using the SMT. The J p 5.5 r 4.5 and 6.5 r 5.5 transitions at 240
and 284 GHz are displayed; each transition is split into two features due to
the lambda-doubling that is readily visible in the spectra. In addition, each
doublet consists of two hyperne components, separated by 611 MHz, that
are not resolved. Positions and relative intensities of the hyperne lines are
shown under each spectrum, assuming V
LSR
p 26 km s
1
, centered at 240,050
and 280,685 MHz. The data have been Hanning-smoothed to 2 MHz resolution
(2.1 km s
1
in the upper spectrum and 2.5 km s
1
in the lower spectrum). The
line proles closely resemble those of SiO and PN found in this source; they
do not contain the blue- and redshifted wings prominent in sulfur-bearing
molecules, as exhibited by the transition of SO
2
in the 284 GHz 16 r 15
0, 16 1, 15
spectrum. These data were acquired in 18 hr (240 GHz) and 21 hr (284 GHz)
of integration time.
phosphorus has a spin of , causing each lambda-doublet
1
I p
2
to further separate into two hyperne components. In the rota-
tional transitions measured here, the hyperne splittings in each
doublet are on the order of 611 MHz, or 714 km s
1
at the
observing frequencies. Given the typical line widths observed
in VY CMa ( km s
1
; e.g., Kemper et al. 2003; DV 4070
1/2
Ziurys et al. 2007), these hyperne components cannot be re-
solved. However, the lambda-doublets are split by 190 MHz
or 220 km s
1
and should be clearly separated in frequency in
this source.
Figure 1 presents the data for PO obtained toward VY CMa.
As shown in the gure, the lambda-doublets of both rotational
transitions are readily visible in the spectra, although the hy-
perne components are blended. Relative positions and inten-
sities of the hyperne components are marked in the gure.
The observed transitions clearly match the expected spectral
pattern of this
2
P radical.
The possibility of contaminating features from other mole-
cules was examined by searching available spectral line cata-
logs as well as the spectroscopy literature. The only feasible
transitions that exist near the PO frequencies arise from
33
SO
2
(the solar
33
S/
32
S isotope ratio is 0.008). These lines are the
hyperne components of the J
Ka, Kc
p 20
1, 19
r 20
0, 20
transition
at 283,795 and 283,802 MHz, and they lie at 199 K above
ground state. While one of these components could lie within
the PO line prole, the other one is far enough away in fre-
quency that it should be a discernable feature. It is clearly not
present in the spectrum. Therefore,
33
SO
2
is not a contaminant.
Interestingly, the lambda-doublets of the tran- J p 13.5 r 12.5
sition of PS at 240,076 and 239,703 MHz lie in the bandpass
of the spectrum of the transition of PO. There J p 5.5 r 4.5
are no obvious features in our spectrumat these frequencies (see
Fig. 1).
Line parameters established from these data are listed in
Table 1. As the table illustrates, the line widths of the four
detected features are km s
1
, with the broader DV 5065
1/2
line widths corresponding to the larger hyperne splittings.
LSR velocities are 25 km s
1
, as expected for molecular fea-
tures in VY CMa (e.g., Kemper et al. 2003). Line intensities
are virtually equal between the doublet pairs, as is characteristic
of
2
P species, as well as being consistent between the two
transitions ( mK).

T 712
A
4. DISCUSSION
4.1. Abundance and Distribution of PO in VY CMa
As discussed in Ziurys et al. (2007), multiple outows appear
to be present in the winds of VY CMa, including a spherical-
type wind, a highly collimated blueshifted expansion, and a
more diffuse redshifted ow. There is chemical selectivity
among these regions, as indicated by the variation in the mo-
lecular line proles. Some molecules, such as SiO, appear only
in the spherical outow, while SO
2
is found in the red- and
blueshifted ows. HCN and CO are present in all three regions
(Ziurys et al. 2007).
The line proles of PO suggest that it arises primarily from
the spherical-like ow. Considering the 714 km s
1
of broad-
ening due to the hyperne structure, the line widths are 40
50 km s
1
, and the shapes are roughly triangular, resembling
those of SiO and PN (Ziurys et al. 2007). The sharp blue- and
redshifted wings that dominate SO
2
proles are not apparent
in the PO spectrum.
The angular extent of PN in VY CMa is approximately 1,
corresponding to a radius of 10
16
cm or 50 stellar radii at
1.5 kpc (stellar radius of 2 # 10
14
cm; Monnier et al. 2000).
Given the similarity in line proles between POand PN, a source
size of roughly 1 can be assumed for phosphorus monoxide.
This value is consistent with the relative intensities of the two
observed transitions and the failure to detect the 2 mm lines of
No. 1, 2007 IDENTIFICATION OF PHOSPHORUS MONOXIDE IN VY CMa L31
this molecule (the spherical wind in VY CMa has a maximum
extent of 12 in CO; Ziurys et al. 2007).
If a source size of 1 is assumed, then the column density of
PO is estimated to be N
tot
2.8 # 10
15
cm
2
, based on the
two transitions, with a rotational temperature of K. T 45
rot
Given a mass-loss rate of 2 # 10
4
M
,
yr
1
for the spherical
ow (Humphreys et al. 2005; Monnier et al. 2000), the fractional
abundance of PO is , relative to H
2
. For this cal-
8
f 9 #10
culation, the experimentally measured dipole moment of 1.88 D
was used (Kanata et al. 1988). In comparison, the abundance of
PN in VY CMa was found to be (Ziurys et al.
8
f 4 #10
2007), resulting in a PO/PN ratio of approximately 1. Despite
the fact that this star is oxygen-rich, PN appears to be an im-
portant carrier of phosphorus.
4.2. Comparison with Theoretical Predictions
Phosphorus has been the subject of several models of cir-
cumstellar chemistry. In their oxygen-rich model, Willacy &
Millar (1997) predict that PH
3
is the most abundant P-bearing
species, with an abundance of 3 #10
8
. The maximum abun-
dance calculated for PO is , which is achieved
10
f 3 #10
2 # 10
16
cm from the star ( for VY CMa). MacKay &

r 1
Charnley (2001) obtain a similar result, with at
9
f (PO) 10
cm. These authors, however, calculate that PS
16
r 2 #10
should be the most abundant species in an oxygen-rich shell,
with an abundance of at radii !10
16
cm. Neither
8
f 5 #10
model calculates PN to be an important species. Both com-
putations start with LTE parent abundances and then consider
the effects of neutral-neutral, ion-molecule, and photochemical
processes.
Because PO and PN appear to be conned to the inner part
of the circumstellar ow, LTE calculations alone may be more
applicable. The most recent LTE computations are by Agundez
et al. (2007). For an O-rich shell, these authors predict an abun-
dance of PO of at 24 stellar radii (5 # 10
14
cm for
7
f 10
VY CMa). This value is close to the observed abundance. In
fact, according to this model, PO is the most abundant species
until 4 stellar radii, where it is converted to P
4
O
6
. If the abundance
of PO freezes out as a parent molecule (McCabe et al. 1979),
then LTE chemistry may explain its abundance in VY CMa. On
the other hand, in the same LTE model, the predicted abundance
of PN is about 2 orders of magnitude less than the
10
f 10
observed concentration. The calculated PN/PO ratio from the
model is thus 1/1000far from the observed value.
4.3. Implications for Phosphorus Chemistry
Current models of circumstellar chemistry do not appear to
reproduce the observed abundances of the phosphorus-bearing
species in VY CMa. On a qualitative level, the models do
suggest that PO is an important species for O-rich circumstellar
shells, but none consider PN as equally dominant. On the other
hand, VY CMa, a 25 M
,
supergiant with T
eff
3000 K, is
more active and luminous than the typical AGB star (Monnier
et al. 2000). The object has additional asymmetric outows
that are likely to be causing shocks (Smith et al. 2001; Hum-
phreys et al. 2005; Ziurys et al. 2007). Hence, the chemistry
that may be more relevant in this object is that proposed by
Cherchneff (2006)a mixed type where LTE abundances
are modied by shocks. VY CMa in fact shows characteristics
of the mixed model, with a relatively high HCN abundance
for an oxygen-rich star (Ziurys et al. 2007). Also, such a model
may account for the presence of PO, a free radical, at larger
stellar radii than suggested by the LTE calculations. However,
phosphorus-bearing species have yet to be incorporated into
such a scheme.
Another factor perhaps inuencing the abundance of PO and
PN in VY CMa is the molecular composition of the spherical
ow. Neglecting O
2
and N
2
, oxygen appears to be contained
primarily in H
2
O, CO, and SiO, all of which are highly abun-
dant in this region, while the principal carrier of nitrogen is
HCN (Ziurys et al. 2007). HCN can only form if there is
sufcient carbon. Consequently, there may not be enough free
oxygen to bond to the available phosphorus and create PO, and
PN thus forms as an alternative, with the excess nitrogen. CS,
SiS, and H
2
S are the most abundant carriers of sulfur in the
spherical wind, perhaps making PS not a viable sink for the
phosphorus. The presence of relatively large abundances of CS
and HCN is usually not considered in models of O-rich en-
velopes and, therefore, may alter chemical outcomes. In fact,
Millar et al. (1987) predict that PN should be present in O-
rich shells that are abundant in HCN.
In VY CMa, both PO and PN disappear earlier in the outow
than molecules such as HCN and HCO

(Ziurys et al. 2007).

The conned nature of phosphorus chemistry is evident in the
carbon-rich shell of IRC 10216 as well (Agundez et al. 2007).
The P-bearing molecules probably condense into dust grains
in both sources, suggesting that phosphorus acts as a refractory
element. Analysis of meteorites (Pasek & Lauretta 2005) and
condensation calculations (Lodders & Fegley 1999) suggest
that schreibersite, (Fe, Ni)
3
P, is the most prominent solid-state
form of phosphorus in both oxygen- and carbon-rich environ-
ments. Studies of molecules such as FeP and NiP could be
extremely useful in establishing the connection between species
such as PO and PN and phosphorus-containing grains.
We thank the ARO telescope operators and engineers for
enabling us to conduct these observations. This research is
supported by NSF grant AST-0607803 and the NASA Astro-
biology Institute under cooperative agreement CAN-02-OSS-
02 issued through the Ofce of Space Science. E. D. T. ac-
knowledges nancial support from the NSF Graduate Research
Fellowship Program.
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