En komparativ analyse av de teoretiske prinsippene for gjennomføringen av norsk defensiv og russisk offensiv relativ til hverandre

Hensikten med denne kvalitative studien er å belyse hvilke forhold som må utnyttes for at prinsippene for norsk defensiv og russisk offensiv skal lykkes relativ til hverandre. Den russiske invasjonen av Ukraina har vist at den konvensjonelle landstriden med defensive og offensive operasjoner fremdeles er gjeldende. Samtidig har den russisk-ukrainske krigen ført til en forverring av forholdet mellom NATO og Russland, og tilsvarende økt spenning i nordområdene. Denne endringen i det norske trusselbildet har igjen økt relevansen for den norske Hærens evne til å forsvare våre nordligste landterritorier. Studien er gjennomført som en komparativ analyse, der en norsk og en russisk tilnærming har blitt kategorisert og analysert innenfor feltfunksjonene ild, manøver og mobilitet/anti-mobilitet. Den norsk defensiven baseres på Forsvarets Doktrine for Landoperasjoner og den russisk offensiven på Doktrine for forberedelser og gjennomføring av samvirkestrid, del 2 (bataljon, kompani). Analysen er gjennomført to-delt: Først en del-drøfting som har tatt for seg punktene: russisk ild sett opp mot norsk manøver, russisk manøver sett opp mot norsk ild, og russisk mobilitet sett opp mot norsk anti-mobilitet. Deretter en samlet drøfting som har sett på hele tilnærmingen i lys av ild, manøver og mobilitet/anti-mobilitet. En norsk defensiv vektlegger en helhetlig plan som balanserer defensive prinsipper der forsvaret skal utføres dynamisk og aggressivt for å rive opp angrepet. Ild skal brukes kontinuerlig i hele operasjonsområdet, manøveren skal være dynamisk og anti-mobilitetstiltak skal etableres i dybde. Russisk offensiv vektlegger risikovillighet og en aggressivitet for å oppnå gjennombrudd og manøver mot dypet av fienden. Ild er hovedverktøyet for å nedkjempe en forsvarende styrke, der manøver og mobilitet skal muliggjøre bruken av ild. Funnene i denne studien viser at det er særlig utnyttelsen av to forhold som påvirker hvorvidt den ene eller andre siden lykkes. Norsk defensiv sin evne til å kunne sinke, stanse og nedkjempe en russisk offensiv påvirkes i stor grad av lendet og hvordan det utnyttes. Skal den russiske offensiven lykkes fordrer det effektiv utnyttelse av ilden, særlig den indirekte, samt at den fysiske mengden med ressurser organiseres og utnyttes slik at et overlegent tempo i manøveren mot dypet kan opprettholdes

Unimolecular Reactions Following Indoor and Outdoor Limonene Ozonolysis

Limonene is one of the monoterpenes with the largest biogenic emissions and is also widely used as an additive in cleaning products, leading to significant indoor emissions. Studies have found that the formation of secondary organic aerosols (SOAs) from limonene oxidation has important implications for indoor air quality. Although ozonolysis is considered the major limonene oxidation pathway under most indoor conditions, little is known about the mechanisms for SOA formation from limonene ozonolysis. Here, we calculate the rate coefficients of the possible unimolecular reactions of the first-generation peroxy radicals formed by limonene ozonolysis using a high-level multiconformer transition state theory approach. We find that all of the peroxy radicals formed initially in the ozonolysis of limonene react unimolecularly with rates that are competitive both indoors and outdoors, except under highly polluted conditions. Differences in reactivity between the peroxy radicals from ozonolysis and those formed by OH, NO₃, and Cl oxidation are discussed. Finally, we sketch possible oxidation mechanisms for the different peroxy radicals under both indoor and pristine atmospheric conditions and in more polluted environments. In environments with low concentrations of HO₂ and NO, efficient autoxidation will lead to the formation of highly oxygenated organic compounds and thus likely aid in the growth of SOA

Stereoselectivity in Atmospheric Autoxidation

We show that the diastereomers of hydroxy peroxy radicals formed from OH and O_2 addition to C2 and C3, respectively, of crotonaldehyde (CH_3CHCHCHO) undergo gas-phase unimolecular aldehydic hydrogen shift (H-shift) chemistry with rate coefficients that differ by an order of magnitude. The stereospecificity observed here for crotonaldehyde is general and will lead to a significant diastereomeric-specific chemistry in the atmosphere. This enhancement of specific stereoisomers by stereoselective gas-phase reactions could have widespread implications given the ubiquity of chirality in nature. The H-shift rate coefficients calculated using multiconformer transition state theory (MC-TST) agree with those determined experimentally using stereoisomer-specific gas-chromatography chemical ionization mass spectroscopy (GC–CIMS) measurements

Unimolecular Reactions of Peroxy Radicals Formed in the Oxidation of α-pinene and β-pinene by Hydroxyl Radicals

Atmospheric oxidation of monoterpenes (emitted primarily by evergreen trees) is known to contribute to the formation and growth of aerosol particles. While recent research has tied the formation of organic aerosol to unimolecular chemistry of the organic peroxy radicals (RO_2) formed in the oxidation of monoterpenes, the fundamental physical chemistry of these RO_2 remains obscure. Here we use isomer-specific measurements and ab initio calculations to determine the unimolecular reaction rates and products of RO_2 derived from the hydroxyl radical (OH) oxidation of α-pinene and β-pinene. Among all of the structural isomers of the first-generation RO_2 from both monoterpenes, we find that the first-generation RO_2 produced following opening of the four-membered ring undergo fast unimolecular reactions (4 ± 2 and 16 ± 5 s^(–1) for α-pinene and β-pinene, respectively) at 296 K, in agreement with high-level ab initio calculations. The presence of the hydroxy group and carbon–carbon double bond in the ring-opened RO_2 enhances the rates of these unimolecular reactions, including endo-cyclization and H-shift via transition states involving six- and seven-membered rings. These reaction rate coefficients are sufficiently large that unimolecular chemistry is the dominant fate of these monoterpene-derived RO_2 in the atmosphere. In addition, the overall yields of first-generation α-pinene and β-pinene hydroxy nitrates, C_(10)H_(17)NO_4, at 296 K and 745 Torr are measured to be 3.3 ± 1.5% and 6.4 ± 2.1%, respectively, for conditions where all RO_2 are expected to react with NO ([NO] > 1000 ppbv). These yields are lower than anticipated

Atmospheric Fate of Methacrolein. 2. Formation of Lactone and Implications for Organic Aerosol Production

We investigate the oxidation of methacryloylperoxy nitrate (MPAN) and methacrylicperoxy acid (MPAA) by the hydroxyl radical (OH) theoretically, using both density functional theory [B3LYP] and explicitly correlated coupled cluster theory [CCSD(T)-F12]. These two compounds are produced following the abstraction of a hydrogen atom from methacrolein (MACR) by the OH radical. We use a RRKM master equation analysis to estimate that the oxidation of MPAN leads to formation of hydroxymethyl–methyl-α-lactone (HMML) in high yield. HMML production follows a low potential energy path from both MPAN and MPAA following addition of OH (via elimination of the NO_3 and OH from MPAN and MPAA, respectively). We suggest that the subsequent heterogeneous phase chemistry of HMML may be the route to formation of 2-methylglyceric acid, a common component of organic aerosol produced in the oxidation of methacrolein. Oxidation of acrolein, a photo-oxidation product from 1,3-butadiene, is found to follow a similar route generating hydroxymethyl-α-lactone (HML)

Atmospheric Fate of Methacrolein. 1. Peroxy Radical Isomerization Following Addition of OH and O_2

Peroxy radicals formed by addition of OH and O_2 to the olefinic carbon atoms in methacrolein react with NO to form methacrolein hydroxy nitrate and hydroxyacetone. We observe that the ratio of these two compounds, however, unexpectedly decreases as the lifetime of the peroxy radical increases. We propose that this results from an isomerization involving the 1,4-H-shift of the aldehydic hydrogen atom to the peroxy group. The inferred rate (0.5 ± 0.3 s^(–1) at T = 296 K) is consistent with estimates obtained from the potential energy surface determined by high level quantum calculations. The product, a hydroxy hydroperoxy carbonyl radical, decomposes rapidly, producing hydroxyacetone and re-forming OH. Simulations using a global chemical transport model suggest that most of the methacrolein hydroxy peroxy radicals formed in the atmosphere undergo isomerization and decomposition

Stereoselectivity in Atmospheric Autoxidation

We show that the diastereomers of hydroxy peroxy radicals formed from OH and O_2 addition to C2 and C3, respectively, of crotonaldehyde (CH_3CHCHCHO) undergo gas-phase unimolecular aldehydic hydrogen shift (H-shift) chemistry with rate coefficients that differ by an order of magnitude. The stereospecificity observed here for crotonaldehyde is general and will lead to a significant diastereomeric-specific chemistry in the atmosphere. This enhancement of specific stereoisomers by stereoselective gas-phase reactions could have widespread implications given the ubiquity of chirality in nature. The H-shift rate coefficients calculated using multiconformer transition state theory (MC-TST) agree with those determined experimentally using stereoisomer-specific gas-chromatography chemical ionization mass spectroscopy (GC–CIMS) measurements

Unimolecular Reactions of Peroxy Radicals Formed in the Oxidation of α-pinene and β-pinene by Hydroxyl Radicals

Atmospheric oxidation of monoterpenes (emitted primarily by evergreen trees) is known to contribute to the formation and growth of aerosol particles. While recent research has tied the formation of organic aerosol to unimolecular chemistry of the organic peroxy radicals (RO_2) formed in the oxidation of monoterpenes, the fundamental physical chemistry of these RO_2 remains obscure. Here we use isomer-specific measurements and ab initio calculations to determine the unimolecular reaction rates and products of RO_2 derived from the hydroxyl radical (OH) oxidation of α-pinene and β-pinene. Among all of the structural isomers of the first-generation RO_2 from both monoterpenes, we find that the first-generation RO_2 produced following opening of the four-membered ring undergo fast unimolecular reactions (4 ± 2 and 16 ± 5 s^(–1) for α-pinene and β-pinene, respectively) at 296 K, in agreement with high-level ab initio calculations. The presence of the hydroxy group and carbon–carbon double bond in the ring-opened RO_2 enhances the rates of these unimolecular reactions, including endo-cyclization and H-shift via transition states involving six- and seven-membered rings. These reaction rate coefficients are sufficiently large that unimolecular chemistry is the dominant fate of these monoterpene-derived RO_2 in the atmosphere. In addition, the overall yields of first-generation α-pinene and β-pinene hydroxy nitrates, C_(10)H_(17)NO_4, at 296 K and 745 Torr are measured to be 3.3 ± 1.5% and 6.4 ± 2.1%, respectively, for conditions where all RO_2 are expected to react with NO ([NO] > 1000 ppbv). These yields are lower than anticipated

Kinetics and Product Yields of the OH Initiated Oxidation of Hydroxymethyl Hydroperoxide

Hydroxymethyl hydroperoxide (HMHP), formed in the reaction of the C1 Criegee intermediate with water, is among the most abundant organic peroxides in the atmosphere. Although reaction with OH is thought to represent one of the most important atmospheric removal processes for HMHP, this reaction has been largely unstudied in the laboratory. Here, we present measurements of the kinetics and products formed in the reaction of HMHP with OH. HMHP was oxidized by OH in an environmental chamber; the decay of the hydroperoxide and the formation of formic acid and formaldehyde were monitored over time using CF3O- chemical ionization mass spectrometry (CIMS) and laser induced fluorescence (LIF). The loss of HMHP by reaction with OH is measured relative to the loss of 1,2-butanediol [k1;2-butanediol+OH = (27:0 5:6) 10- exp12 cm3 molecule-1s-1]. We find that HMHP reacts with OH at 295 K with a rate coefficient of (7.1 1.5) 10-12 cm3 molecule-1s-1, with the formic acid to formaldehyde yield in a ratio of 0:880:21 and independent of NO concentration (31010 1.51013 molecule cm-3). We suggest that, exclusively, abstraction of the methyl hydrogen of HMHP results in formic acid while abstraction of the hydroperoxy hydrogen results in formaldehyde. We further evaluate the relative importance of HMHP sinks and use global simulations from GEOS-Chem to estimate that HMHP oxidation by OH contributes 1.7 Tg yr-1 (1-3%) of global annual formic acid production