Systematization of published spectral data on ...

Systematization of published spectral data on deuterated isotopologues of hydrogen sulfide molecule Voronina S.S., Naumenko O.V., Polovtseva E.R., Fazliev A.Z. Institute of Atmospheric Optics SB RAS, Academician Zuev Sq., 1, Tomsk 634055, Russia ABSTRACT The report presents a description of properties of published data on spectral lines parameters of deuterated isotopologues of hydrogen sulfide - HDS, HD34S, D2S, D234S. Properties values characterizing data quality are calculated taking into account the validity criteria and credit estimation according to publishing criteria. Formalized criteria of data check based on the constraints and selection rules known from the vibrational-rotational theory, as well as an expert evaluation are utilized for validation of the original experimental transitions and energy levels. The consistent and accurate set of the vibration - rotation (VR) energy levels is derived based on the cleaned transitions. Published vibrational-rotational transitions and energy levels of considered molecules as well as the knowledge base are available in the Internet in W@DIS information system (IS). Keywords: Deuterated isotopologues of hydrogen sulfide, W@DIS information system, rotation-vibrational transitions, energy levels.

1. INTRODUCTION The study of the hydrogen sulfide spectra and its deuterated species is important for applications in physics, chemistry, etc. Spectral properties of hydrogen sulfide deuterated isotopologues are of great interest to the researchers of Venus atmosphere and interstellar space as presence of D2S molecule in interstellar space has already been proved. These isotopologues have been studied already for about 80 years though the number of publications on this topic is slightly more than 40 with the last review article published in 1973. Earlier, the work on systematization of the published vibration- rotation transitions and energy levels for three main isotopologues of the hydrogen sulfide – H232S, H233S, and H234S has been completed1. This report presents a review of spectral data on HDS, HD34S, D2S, D234S molecules collected and imported in IS W@DIS revealing the disagreement of published values of vacuum wavenumbers. We will focus, mainly, on the main principles and software used in W@DIS for processing the experimental data from different experimental sources. Ontology automatically provides answers to a major part of queries about the quality of data available in information system. The data properties in the information system are presented in two forms: as triads in the database and as statements written in the XML-syntax of OWL DL language2 in the knowledge base3. The necessity to use and develop Internet accessible information systems is conditioned by their ability to grant data, information and knowledge partitioning to scientific community. This ability allows one to quickly set actual measuring and calculation tasks with a possibility to check formal constraints and task solution correlation calculation with all published solutions in a short period of time and in an accessible way. Quick reaction of researchers to the quality of data, information and knowledge stored in data bases leads to the improvement of all of these components of information resources. In order to get an adequate back reaction it is necessary for a researcher to understand the basis of the information- computational system (ICS) formation and functioning. In this chapter the semantics of basic concepts in the framework of their use at threelayer IS architecture development is introduced and demonstrated on the example of W@DIS ICS. Physical entities and values of their properties were united into sets with the meaning of spectroscopy tasks solutions. Two chains of tasks were selected among all spectroscopy tasks. This model of molecular spectroscopy proved to be useful for the development of the IS oriented on the collection and formation of reliable sets of tasks solutions. A researcher may decompose any expert set of data, for example, on water spectroscopy into basic data sets published in press and in Internet. 20th International Symposium on Atmospheric and Ocean Optics: Atmospheric Physics, edited by Gennadii G. Matvienko, Oleg A. Romanovskii, Proc. of SPIE Vol. 9292, 92920B · © 2014 SPIE · CCC code: 0277-786X/14/$18 · doi: 10.1117/12.2075976 Proc. of SPIE Vol. 9292 92920B-1

Working with water spectroscopy logical theory we had to make a constraint due to a great amount of knowledge obtained in the process of calculation. The operation of databases that contain dozens of billions of values requires high performance of servers they are stored on. The work done in Institute of Atmospheric Optics (IAO SB RAS) revealed that the selection from database and the simplest processing of one million records takes about one minute if we use a server with 16 Gb RAM and two quadro-core processors. The processing of billions of records requires greater RAM memory space and rate of data exchange between RAM and hard disk drive (HDD) sets. That is why forming factual part of applied ontology the calculated values were omitted. 2.

INFORMATION RESOURCES COLLECTION

The first stage implied the collection of publications containing data on hydrogen sulfide isotpologues. At this stage the section of digital library containing more than 50 articles was developed and the values of physical quantities were extracted and uploaded into files. The data from one publication related to a single molecule and to the solution of one of the three tasks of spectroscopy (Т1, Т7 – direct and inverted tasks on determining the energy levels correspondingly, Т6 – inverted task on the determination of vacuum wave numbers1) were uploaded into one file. At the second stage information sources containing both data source and machine description of imported data properties were automatically formed. The statistics of data on hydrogen sulfide molecule deuterated isotopologues and tasks are presented in Table 1. The number of information sources, as well as the total number of states or transitions extracted from publications is shown for each isotopologue. Table1. The number of sources and data on hydrogen sulfide deuterated isotopologues imported from these sources (divided according to the spectroscopy tasks). Substance D2S HDS D234S HD34S Total

T1 5 / 332 5 / 3126 10/ 3458

Spectroscopy tasks T6 6 / 867 6 / 3197 1 /64 2 / 95 13/ 4223

T7 5 / 3401 7 / 6114 2 /2 1 /68 15 / 9585

In the reviewed articles the majority of energy levels are identified from experimental data though there are some calculated levels. The majority of articles have no values of experimental vacuum wave numbers. Table 2 presents the information on vibrational-rotational transitions and energy levels for various vibrational bands and states for four hydrogen sulfide isotopologues. Figure 1 shows the properties of the whole set of 407 vacuum quantum numbers of D2S molecule published in paper4. The quantum numbers of the corresponding transitions satisfy all constraints on the states and rules of selection. Binary relations between data sources are described in the bottom-right of the table. In the top line of this part lists the names and the location of each property in the table cell. Data source 1985_CaFlLeJo_ D2S has identical transitions with three other data sources. Each pair is characterized by seven properties. The first property is the maximum value of the difference between the vacuum quantum numbers of identical transitions Δωmax (Δωmax