48 research outputs found
Alkali and Alkaline Earth Metal Compounds: Core-Valence Basis Sets and Importance of Subvalence Correlation
Core-valence basis sets for the alkali and alkaline earth metals Li, Be, Na,
Mg, K, and Ca are proposed. The basis sets are validated by calculating
spectroscopic constants of a variety of diatomic molecules involving these
elements. Neglect of correlation in K and Ca compounds will lead to
erratic results at best, and chemically nonsensical ones if chalcogens or
halogens are present. The addition of low-exponent functions to the K and
Ca basis sets is essential for smooth convergence of molecular properties.
Inclusion of inner-shell correlation is important for accurate spectroscopic
constants and binding energies of all the compounds. In basis set
extrapolation/convergence calculations, the explicit inclusion of alkali and
alkaline earth metal subvalence correlation at all steps is essential for K and
Ca, strongly recommended for Na, and optional for Li and Mg, while in Be
compounds, an additive treatment in a separate `core correlation' step is
probably sufficient. Consideration of inner-shell correlation energy in
first-row elements requires inclusion of `deep core' correlation
energy in K and Ca for consistency. The latter requires special CCVZ `deep
core correlation' basis sets. For compounds involving Ca bound to
electronegative elements, additional functions in the basis set are
strongly recommended. For optimal basis set convergence in such cases, we
suggest the sequence CV(D+3d)Z, CV(T+2d)Z, CV(Q+)Z, and CV5Z on calcium.Comment: Molecular Physics, in press (W. G. Richards issue); supplementary
material (basis sets in G98 and MOLPRO formats) available at
http://theochem.weizmann.ac.il/web/papers/group12.htm
ПРО ОДИН З АСПЕКТІВ КОМПЛЕКСНОГО ВИРІШЕННЯ ПИТАННЯ БУДІВНИЦТВА КАНАЛУ АЗОВСЬКЕ МОРЕ – МОЛОЧНИЙ ЛИМАН
Молочний лиман – один з найбільш цінних водно-болотних угідь Приа-зов’я, який увійшов до Міжнародного кадастру Рамсарських територій. Згідно з фізико-географічним районуванням України, Молочний лиман відноситься до Присивасько-Приазовської степової області Причорноморської південно-степової провінції. Адміністративно ця акваторія знаходиться в Запорізькій об-ласті і розташована на територіях Якимівського, Приазовського та Мелітополь-ського районів. Довжина лиману складає 32 км, максимальна ширина 8 км, гли-бина до 3 м, площа 170 км2. Від Азовського моря Лиман відділений косою Пе-ресип зі штучно створеною протокою (промоїною). Останнім часом, з`єднувальний канал Молочного лиману практично не функціонує
HIFI spectroscopy of low-level water transitions in M82
We present observations of the rotational ortho-water ground transition, the
two lowest para-water transitions, and the ground transition of ionised
ortho-water in the archetypal starburst galaxy M82, performed with the HIFI
instrument on the Herschel Space Observatory. These observations are the first
detections of the para-H2O(111-000) (1113\,GHz) and ortho-H2O+(111-000)
(1115\,GHz) lines in an extragalactic source. All three water lines show
different spectral line profiles, underlining the need for high spectral
resolution in interpreting line formation processes. Using the line shape of
the para-H2O(111-000) and ortho-H2O+(111-000) absorption profile in conjunction
with high spatial resolution CO observations, we show that the (ionised) water
absorption arises from a ~2000 pc^2 region within the HIFI beam located about
~50 pc east of the dynamical centre of the galaxy. This region does not
coincide with any of the known line emission peaks that have been identified in
other molecular tracers, with the exception of HCO. Our data suggest that water
and ionised water within this region have high (up to 75%) area-covering
factors of the underlying continuum. This indicates that water is not
associated with small, dense cores within the ISM of M82 but arises from a more
widespread diffuse gas component.Comment: 5 pages, 4 figures. Accepted for publication in A&
Herschel/HIFI observations of interstellar OH+ and H2O+ towards W49N: a probe of diffuse clouds with a small molecular fraction
We report the detection of absorption by interstellar hydroxyl cations and
water cations, along the sight-line to the bright continuum source W49N. We
have used Herschel's HIFI instrument, in dual beam switch mode, to observe the
972 GHz N = 1 - 0 transition of OH+ and the 1115 GHz 1(11) - 0(00) transition
of ortho-H2O+. The resultant spectra show absorption by ortho-H2O+, and strong
absorption by OH+, in foreground material at velocities in the range 0 to 70
km/s with respect to the local standard of rest. The inferred OH+/H2O+
abundance ratio ranges from ~ 3 to ~ 15, implying that the observed OH+ arises
in clouds of small molecular fraction, in the 2 - 8% range. This conclusion is
confirmed by the distribution of OH+ and H2O+ in Doppler velocity space, which
is similar to that of atomic hydrogen, as observed by means of 21 cm absorption
measurements, and dissimilar from that typical of other molecular tracers. The
observed OH+/H abundance ratio of a few E-8 suggests a cosmic ray ionization
rate for atomic hydrogen of (0.6 - 2.4) E-16 s-1, in good agreement with
estimates inferred previously for diffuse clouds in the Galactic disk from
observations of interstellar H3+ and other species.Comment: Accepted for publication in A&A Letter
Herschel-HIFI detections of hydrides towards AFGL 2591 (Envelope emission versus tenuous cloud absorption)
The Heterodyne Instrument for the Far Infrared (HIFI) onboard the Herschel
Space Observatory allows the first observations of light diatomic molecules at
high spectral resolution and in multiple transitions. Here, we report deep
integrations using HIFI in different lines of hydrides towards the high-mass
star forming region AFGL 2591. Detected are CH, CH+, NH, OH+, H2O+, while NH+
and SH+ have not been detected. All molecules except for CH and CH+ are seen in
absorption with low excitation temperatures and at velocities different from
the systemic velocity of the protostellar envelope. Surprisingly, the CH(JF,P =
3/2_2,- - 1/2_1,+) and CH+(J = 1 - 0, J = 2 - 1) lines are detected in emission
at the systemic velocity. We can assign the absorption features to a foreground
cloud and an outflow lobe, while the CH and CH+ emission stems from the
envelope. The observed abundance and excitation of CH and CH+ can be explained
in the scenario of FUV irradiated outflow walls, where a cavity etched out by
the outflow allows protostellar FUV photons to irradiate and heat the envelope
at larger distances driving the chemical reactions that produce these
molecules.Comment: Accepted for publication in Astronomy and Astrophysics (HIFI first
results issue
Herschel/HIFI observations of spectrally resolved methylidyne signatures toward the high-mass star-forming core NGC6334I
In contrast to extensively studied dense star-forming cores, little is known
about diffuse gas surrounding star-forming regions. We study molecular gas in
the high-mass star-forming region NGC6334I, which contains diffuse, quiescent
components that are inconspicuous in widely used molecular tracers such as CO.
We present Herschel/HIFI observations of CH toward NGC6334I observed as part of
the CHESS key program. HIFI resolves the hyperfine components of its J=3/2-1/2
transition, observed in both emission and absorption. The CH emission appears
close to the systemic velocity of NGC6334I, while its measured linewidth of 3
km/s is smaller than previously observed in dense gas tracers such as NH3 and
SiO. The CH abundance in the hot core is 7 10^-11, two to three orders of
magnitude lower than in diffuse clouds. While other studies find distinct
outflows in, e.g., CO and H2O toward NGC6334I, we do not detect outflow
signatures in CH. To explain the absorption signatures, at least two absorbing
components are needed at -3.0 and +6.5 km/s with N(CH)=7 10^13 and 3 10^13
cm^-2. Two additional absorbing clouds are found at +8.0 and 0.0 km/s, both
with N(CH)=2 10^13 cm^-2. Turbulent linewidths for the four absorption
components vary between 1.5 and 5.0 km/s in FWHM. We constrain physical
properties of our CH clouds by matching our CH absorbers with other absorption
signatures. In the hot core, molecules such as H2O and CO trace gas that is
heated and dynamically influenced by outflow activity, whereas CH traces more
quiescent material. The four CH absorbers have column densities and turbulent
properties consistent with diffuse clouds: two are located near NGC6334, and
two are unrelated foreground clouds. Local density and dynamical effects
influence the chemical composition of physical components of NGC6334, causing
some components to be seen in CH but not in other tracers, and vice versa.Comment: Accepted by A&A Letters; 5 pages, 1 figure; v2: minor textual and
typographical change
Detection of interstellar oxidaniumyl: abundant H2O+ towards the star-forming regions DR21, Sgr B2, and NGC6334
We identify a prominent absorption feature at 1115 GHz, detected in first
HIFI spectra towards high-mass star-forming regions, and interpret its
astrophysical origin. The characteristic hyperfine pattern of the H2O+
ground-state rotational transition, and the lack of other known low-energy
transitions in this frequency range, identifies the feature as H2O+ absorption
against the dust continuum background and allows us to derive the velocity
profile of the absorbing gas. By comparing this velocity profile with velocity
profiles of other tracers in the DR21 star-forming region, we constrain the
frequency of the transition and the conditions for its formation. In DR21, the
velocity distribution of H2O+ matches that of the [CII] line at 158\mu\m and of
OH cm-wave absorption, both stemming from the hot and dense clump surfaces
facing the HII-region and dynamically affected by the blister outflow. Diffuse
foreground gas dominates the absorption towards Sgr B2. The integrated
intensity of the absorption line allows us to derive lower limits to the H2O+
column density of 7.2e12 cm^-2 in NGC 6334, 2.3e13 cm^-2 in DR21, and 1.1e15
cm^-2 in Sgr B2.Comment: Accepted for publication in A&
Effects of microperfusion in hepatic diffusion weighted imaging
Clinical hepatic diffusion weighted imaging (DWI) generally relies on mono-exponential diffusion. The aim was to demonstrate that mono-exponential diffusion in the liver is contaminated by microperfusion and that the bi-exponential model is required. Nineteen fasting healthy volunteers were examined with DWI (seven b-values) using fat suppression and respiratory triggering (1.5 T). Five different regions in the liver were analysed regarding the mono-exponentially fitted apparent diffusion coefficient (ADC), and the bi-exponential model: molecular diffusion (D (slow) ) microperfusion (D (fast) ) and the respective fractions (f (slow/fast)). Data were compared using ANOVA and Kruskal-Wallis tests. Simulations were performed by repeating our data analyses, using just the DWI series acquired with b-values approximating those of previous studies. Median mono-exponentially fitted ADCs varied significantly (P <0.001) between 1.107 and 1.423 x 10(-3) mm(2)/s for the five regions. Bi-exponential fitted D-slow varied between 0.923 and 1.062 x 10(-3) mm(2)/s without significant differences (P = 0.140). D (fast) varied significantly, between 17.8 and 46.8 x 10(-3) mm(2)/s (P <0.001). F-tests showed that the diffusion data fitted the bi-exponential model significantly better than the mono-exponential model (F > 21.4, P <0.010). These results were confirmed by the simulations. ADCs of normal liver tissue are significantly dependent on the measurement location because of substantial microperfusion contamination; therefore the bi-exponential model should be used. Diffusion weighted MR imaging helps clinicians to differentiate tumours by diffusion properties Fast moving water molecules experience microperfusion, slow molecules diffusion Hepatic diffusion should be measured by bi-exponential models to avoid microperfusion contamination Mono-exponential models are contaminated with microperfusion, resulting in apparent regional diffusion differences Bi-exponential models are necessary to measure diffusion and microperfusion in the liver
Whole-body diffusion-weighted imaging for staging malignant lymphoma in children
CT is currently the mainstay in staging malignant lymphoma in children, but the risk of second neoplasms due to ionizing radiation associated with CT is not negligible. Whole-body MRI techniques and whole-body diffusion-weighted imaging (DWI) in particular, may be a good radiation-free alternative to CT. DWI is characterized by high sensitivity for the detection of lesions and allows quantitative assessment of diffusion that may aid in the evaluation of malignant lymphomas. This article will review whole-body MRI techniques for staging malignant lymphoma with emphasis on whole-body DWI. Furthermore, future considerations and challenges in whole-body DWI will be discussed