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We present here a new example of chemical reactivity governed by quantum tunneling, which also highlights the limitations of the classical theories. The

The 1H- and 2H-1,2,3-triazoles are isomeric five-membered ring, aromatic heterocycles that may undergo chemical equilibration by virtue of intramolecular hydrogen migration (tautomerization). Using millimeter-wave spectroscopy in the 130-375 GHz frequency range, we measured the spectroscopic constants for thirteen 1H-1,2,3-triazole and sixteen 2H-1,2,3-triazole isotopologues. Herein, we provide highly accurate and highly precise semi-experimental equilibrium (r

Current conceptualizations of oppositional defiant disorder (ODD) place the symptoms of this disorder within three separate but related dimensions (i.e., angry/irritable mood, argumentative/defiant behavior, vindictiveness). Variable-centered models of these dimensions have yielded discrepant findings, limiting their clinical utility. The current study utilized person-centered latent class analysis based on self and parent report of ODD symptomatology from a community-based cohort study of 521 adolescents. We tested for sex, race, and age differences in the identified classes and investigated their ability to predict later symptoms of depression and conduct disorder (CD). Diagnostic information regarding ODD, depression, and CD were collected annually from adolescents (grades 6–9; 51.9% male; 48.7% White, 28.2% Black, 18.5% Asian) and a parent. Results provided evidence for three classes of ODD (high, medium, and low endorsement of symptoms), which demonstrated important developmental differences across time. Based on self-report, Black adolescents were more likely to be in the high and medium classes, while according to parent report, White adolescents were more likely to be in the high and medium classes. Membership in the high and medium classes predicted later increases in symptoms of depression and CD, with the high class showing the greatest risk for later psychopathology.

Maladaptive family environments harm child development and are passed across generations. Childhood interventions may break this intergenerational cycle by improving the family environments children form as adults. The present study investigates this hypothesis by examining follow-up data collected 18 years after the end of the childhood Fast Track intervention designed to prevent externalizing problems.We examined whether Fast Track assignment from grades 1 to 10 prevented the emergence of maladaptive family environments at age 34. A total of 400 (n = 206 in intervention condition, n = 194 controls) Fast Track participants who were parents at age 34 were surveyed about 11 aspects of their current family environment. The hypotheses and analytic plan were preregistered at https://osf.io/dz9t5 and the Fast Track trial was registered at clinicaltrials.gov (NCT01653535).Multiple group linear regression models revealed that mothers who participated in the Fast Track intervention as children had lower depression symptoms, alcohol problems, drug problems, corporal punishment use, and food insecurity compared to control group mothers. All effects were modest in magnitude. However, for these same mothers, the Fast Track intervention had no effect on cannabis problems, experiences of romantic partner violence, or maternal use of physical aggression or warmth with their children. Additionally, mothers in the Fast Track intervention group reported higher levels of family chaos than those in the control group, but this effect may be a byproduct of the higher number of children per household in the intervention group. No intervention effects were found for fathers who participated in the Fast Track intervention as children.Childhood assignment to Fast Track has some beneficial effects for girls, but not boys, on the family environments these individuals formed as adults 18 years later.

Posttraumatic stress disorder (PTSD) and depressive symptoms have been associated with poorer health-related quality of life in adolescents after general traumatic injuries; few studies have examined the broader construct of postinjury quality of life (QOL). We evaluated the impact of traumatic injury on adolescent QOL and examined factors that potentially contribute to poorer outcomes, using the Youth Quality of Life Instrument-Research Version as the outcome measure. Data were collected within 30 days postinjury and 2, 5, and 12 months postinjury. Mixed-model regression (MMR) was used for the main analyses. Participants (N = 204) were drawn from a prospective cohort study of 12-18-year-olds admitted to a Level 1 trauma center (n = 108) and healthy participants from a local cross-sectional study (n = 116); study group participants were significantly older. The initial MMR indicated that female adolescents had significantly lower QOL, B = -2.69, 95% CI [-4.68, -0.70], and were more likely to score above the cutoffs for PTSD (19.1% vs. 2.0%), χ2 (1, N = 381) = 34.6, p

There is growing evidence of diverse etiological pathways to the development of callous-unemotional (CU) traits, known as primary and secondary CU variants. The purpose of the present study was to extend previous cross-sectional research and examine theoretical predictors of CU variants prospectively from childhood to adolescence. Participants included high-risk control and normative samples from the Fast Track project (N = 754, male = 58%, Black = 46%). Using structural equation modelling, primary CU traits, identified in early adolescence, were associated with higher levels of childhood emotion regulation and lower levels of prosocial behavior. Secondary CU traits were associated with lower levels of childhood emotion regulation and low parental warmth, but not prosocial behaviour. Neither CU variant was related to harsh parenting. Parental warmth moderated emotion regulation and prosocial behavior on secondary CU traits. Results were not moderated by sex. A greater understanding of theoretical developmental precursors of CU variants may better guide intervention efforts.

The millimeter/submillimeter spectrum of 1

A semi-experimental equilibrium structure (reSE) of pyridazine (o-C4H4N2) has been determined using the rotational spectra of 18 isotopologues. Spectroscopic constants of four isotopologues are reported for the first time (measured from 235 to 360 GHz), while spectroscopic constants for previously reported isotopologues are improved by extending the frequency coverage (measured from 130 to 375 GHz). The experimental values of the ground-state rotational constants (A0, B0, and C0) from each isotopologue were converted to determinable constants (A0″, B0″, and C0″), which were then corrected for the effects of vibration-rotation interactions and electron-mass distributions using CCSD(T)/cc-pCVTZ calculations. The resultant reSE for pyridazine determines bond distances to within 0.001 A and bond angles within 0.04°, a reduction in the statistical uncertainties by at least a factor of two relative to the previously reported reSE. The improvement in precision appears to be largely due to the use of higher-level theoretical calculations of the vibration-rotation and electron-mass effects, though the incorporation of the newly measured isotopologues ([4-2H, 4-13C]-, [4-2H, 5-13C]-, [4-2H, 6-13C]-, and [4,5-2H, 4-13C]-pyridazine) is partially responsible for the improved determination of the hydrogen-containing bond angles. The computed equilibrium structure (re) (CCSD(T)/cc-pCV5Z) and a "best theoretical estimate" of the equilibrium structure (re) both agree with the updated reSE structure within the statistical experimental uncertainty (2σ) of each structural parameter.

Applying both latent variable and network frameworks, we conducted a comprehensive psychometric evaluation of the diverse array of symptoms from three externalizing dimensions, including attention problems, aggressive behavior, and delinquency/rule-breaking of the Child Behavior Checklist (Achenbach, 1991) across six time points from childhood to early adolescence. We also examined sex differences. Participants (

This study examined whether a key set of adolescent and early adulthood risk factors predicts problematic alcohol, cannabis, and other substance use in established adulthood. Two independent samples from the Child Development Project (CDP; n = 585; 48% girls; 81% White, 17% Black, 2% other race/ethnicity) and Fast Track (FT; n = 463; 45% girls; 52% White, 43% Black, 5% other race/ethnicity) were recruited in childhood and followed through age 34 (CDP) or 32 (FT). Predictors of substance use were assessed in adolescence based on adolescent and parent reports and in early adulthood based on adult self-reports. Adults reported their own problematic substance use in established adulthood. In both samples, more risk factors from adolescence and early adulthood predicted problematic alcohol use in established adulthood (compared to problematic cannabis use and other substance use). Externalizing behaviors and prior substance use in early adulthood were consistent predictors of problematic alcohol and cannabis misuse in established adulthood across samples; other predictors were specific to the sample and type of substance misuse. Prevention efforts might benefit from tailoring to address risk factors for specific substances, but prioritizing prevention of externalizing behaviors holds promise for preventing both alcohol and cannabis misuse in established adulthood.

Hydrazoic acid (HN

Three cyanobutadiene isomers have been synthesized and their rotational spectra analyzed in the 130-375 GHz frequency range. These species, which are close analogues of known interstellar molecules and are isomers of the heterocyclic aromatic molecule pyridine (C5H5N), offer the opportunity of revealing important insights concerning the chemistry in astronomical environments. The s-trans conformers of E-1-cyano-1,3-butadiene and Z-1-cyano-1,3-butadiene are observed, while both the anti-clinal and syn-periplanar conformers of 4-cyano-1,2-butadiene are evident in the rotational spectra. Over 1000 transitions for s-trans-Z-1-cyano-1,3-butadiene and for syn-periplanar-4-cyano-1,2-butadiene are fit to an octic, distorted-rotor Hamiltonian with low uncertainty (

Maternal warmth has been identified as a contributing factor to the development of child anxiety; however, no studies to date have examined observed maternal warmth longitudinally in this relationship. The present study addressed this knowledge gap by examining the simultaneous development of maternal warmth and child anxiety over time (between-person effects using latent growth curve modeling) and the directionality of associations (within-person effects using autoregressive latent trajectory modeling). Participants included 753 mothers and children. Between-person effects indicated that lower initial levels of anxiety were related to greater levels of maternal warmth over time. Within-person effects showed that maternal warmth in grade 1 predicted subsequent decreases in child anxiety in grade 2 (i.e., a parent effect). Present findings demonstrate the importance of maternal warmth in the early school-age years for decreasing subsequent child anxiety.

While phenotypically indistinguishable with respect to callousness, individuals with primary and secondary callous–unemotional (CU) traits may show different developmental outcomes. This research predominantly comprised cross-sectional studies of male participants with a focus on maladaptive correlates. Thus, the present study examined whether youth with primary and secondary CU traits identified in Grade 7 reported distinct maladaptive outcomes (internalizing, externalizing, and substance use problems; criminal offenses; and sexual and partner experiences) and adaptive outcomes (health and wellbeing, education, and employment) in adulthood at age 25. We also examined sex differences. Participants included the high-risk control and normative samples from the Fast Track project (N = 754, male = 58%, Black = 46%). Youth with secondary CU traits reported higher levels of adult internalizing and externalizing psychopathology, a greater number of sexual partners and risky sexual behavior, and a greater number of violent offenses, compared with individuals with primary CU traits and those with low CU and anxiety symptoms. Conversely, youth with primary CU traits and low symptoms had higher wellbeing and happiness scores than those with secondary CU traits. Finally, there was differentiation on outcomes between female primary and secondary CU variants and male primary and secondary CU variants.

Violence exposure during childhood and adolescence is associated with a range of negative psychosocial outcomes. Research examining the impact of violence exposure has been limited by the compartmentalization into separate bodies of research (e.g., community violence, domestic violence). There is also a paucity of research examining long-term adult outcomes. Using a large and racially diverse sample (n = 754; male = 58%; Black = 46%), the current longitudinal study aimed to elucidate the comparative and cumulative effect of different types of violence exposure (witnessing vs. victimization) across different locations (home, school, neighborhood) in childhood and adolescence (lifetime through Grade 8) on long-term internalizing, externalizing, and attention problems; substance use; and intimate partner violence in adulthood (age 25). Victimization, but not witnessing violence, predicted all five adult outcomes. Specifically, being victimized at home was associated with the widest range of negative outcomes (internalizing, externalizing, and attention problems), while school victimization was associated with substance use. Further, when youth experienced multiple types of violence across multiple locations (cumulative violence exposure), they experienced a more diverse range of negative outcomes in adulthood (composite score). The current study highlights the stronger effects of violence exposure in more proximal contexts, and how these locations are important for emotional and behavioral development.

There is ongoing debate regarding whether psychopathy dimensions (i.e., narcissism, callous-unemotional [CU] traits, and impulsivity) can be meaningfully identified among youth samples and the correlates of these components. Thus, the present study conducted confirmatory factor analyses of the parent-reported Antisocial Process Screening Device (APSD; Frick and Hare 2001) among early adolescents, and examined whether trajectories of conduct problems (CP) through childhood were associated with APSD total and subscale scores. Participants included the normative and high-risk control samples from the Fast Track project (N = 754, male = 58%, Black = 46%). Parents reported on CP in kindergarten, grades 1, 2, 4, 5, and 7, and psychopathy in grade 7. Factor analyses supported the three-factor structure. Latent class growth analyses identified four trajectories of CP including extremely high increasing (3.6%), high stable (21.6%), moderate decreasing (38.7%), and low decreasing (36.1%). All CP trajectories were significantly different from each other on psychopathy total, narcissism, and impulsivity scores; the extremely high increasing and high stable trajectories did not differ from each other on CU traits, but they scored significantly higher than the moderate decreasing and low decreasing trajectories. When controlling for other dimensions, all trajectories were significantly different on narcissism. The extremely high increasing and high stable CP trajectories did not differ from each other on impulsivity, but they scored higher than the moderate decreasing and low trajectories. Only the extremely high increasing and high stable trajectories scored higher than the low decreasing trajectory on CU traits.

Not long ago, the occurrence of quantum mechanical tunneling (QMT) chemistry involving atoms heavier than hydrogen was considered unreasonable. Contributing to the shift of this paradigm, we present here the discovery of a new and distinct heavy-atom QMT reaction. Triplet syn-2-formyl-3-fluorophenylnitrene, generated in argon matrices by UV-irradiation of an azide precursor, was found to spontaneously cyclize to singlet 4-fluoro-2,1-benzisoxazole. Monitoring the transformation by IR spectroscopy, temperature-independent rate constants (k≈1.4×10-3 s-1 ; half-life of ≈8 min) were measured from 10 to 20 K. Computational estimated rate constants are in fair agreement with experimental values, providing evidence for a mechanism involving heavy-atom QMT through crossing triplet to singlet potential energy surfaces. Moreover, the heavy-atom QMT takes place with considerable displacement of the oxygen atom, which establishes a new limit for the heavier atom involved in a QMT reaction in cryogenic matrices.

The rotational spectrum of 1-cyanocyclobutene from 130 to 360 GHz has been observed, assigned, and least-squares fit for the ground state and the two lowest-energy vibrationally excited states. Synthesis by UV photochemical dimerization of acrylonitrile and subsequent base-catalyzed dehydrocyanation affords a highly pure sample, yielding several thousand observable rotational transitions for this small organic nitrile. Over 2500

In this work, we present the spectral analysis of 1 H- and 2 H-1,2,3-triazole vibrationally excited states alongside provisional and practical computational predictions of the excited-state quartic centrifugal distortion constants. The low-energy fundamental vibrational states of 1 H-1,2,3-triazole and five of its deuteriated isotopologues ([1-2H]-, [4-2H]-, [5-2H]-, [4,5-2H]-, and [1,4,5-2H]-1 H-1,2,3-triazole), as well as those of 2 H-1,2,3-triazole and five of its deuteriated isotopologues ([2-2H]-, [4-2H]-, [2,4-2H]-, [4,5-2H]-, and [2,4,5-2H]-2 H-1,2,3-triazole), are studied using millimeter-wave spectroscopy in the 130–375 GHz frequency region. The normal and [2-2H]-isotopologues of 2 H-1,2,3-triazole are also analyzed using high-resolution infrared spectroscopy, determining the precise energies of three of their low-energy fundamental states. The resulting spectroscopic constants for each of the vibrationally excited states are reported for the first time. Coupled-cluster vibration–rotation interaction constants are compared with each of their experimentally determined values, often showing agreement within 500 kHz. Newly available coupled-cluster predictions of the excited-state quartic centrifugal distortion constants based on fourth-order vibrational perturbation theory are benchmarked using a large number of the 1,2,3-triazole tautomer isotopologues and vibrationally excited states studied.

There is growing evidence of diverse etiological pathways to the development of callous-unemotional (CU) traits, known as primary and secondary CU variants. The purpose of the present study was to extend previous cross-sectional research and examine theoretical predictors of CU variants prospectively from childhood to adolescence. Participants included high-risk control and normative samples from the Fast Track project (N = 754, male = 58%, Black = 46%). Using structural equation modelling, primary CU traits, identified in early adolescence, were associated with higher levels of childhood emotion regulation and lower levels of prosocial behavior. Secondary CU traits were associated with lower levels of childhood emotion regulation and low parental warmth, but not prosocial behaviour. Neither CU variant was related to harsh parenting. Parental warmth moderated emotion regulation and prosocial behavior on secondary CU traits. Results were not moderated by sex. A greater understanding of theoretical developmental precursors of CU variants may better guide intervention efforts.

A semi-experimental equilibrium structure (

The analysis of syn-2-cyano-1,3-butadiene (C5H5N, μa = 3.2 D, μb = 2.3 D) in its ground vibrational state and two lowest-energy excited vibrational states, ν27 (A″, 144 cm−1) and ν19 (A′, 163 cm−1)...

The pure rotational spectrum of thiazole (c-C(3)H(3)NS, C(s)) has been studied in the millimeter-wave region from 130 to 375 GHz. Nearly 4800 newly measured rotational transitions for the ground vibrational state of the main isotopologue were combined with previously reported measurements and least-squares fit to a complete sextic Hamiltonian. Transitions for six singly substituted heavy-atom isotopologues ((13)C, (15)N, (33)S, (34)S) were observed at natural abundance and likewise fit. Several deuterium-enriched samples were prepared, which gave access to the rotational spectra of 16 additional isotopologues, 14 of which had not been previously studied. The rotational spectra of each isotopologue were fit to A- and S-reduced distorted-rotor Hamiltonians in the I(r) representation. The experimental values of the ground-state rotational constants (A(0), B(0), and C(0)) from each isotopologue were converted to determinable constants (A(0)″, B(0)″, and C(0)″), which were corrected for effects of vibration–rotation interactions and electron-mass distributions using coupled-cluster singles, doubles, and perturbative triples calculations [CCSD(T)/cc-pCVTZ]. The moments of inertia from the resulting constants (A(e), B(e), and C(e)) of 24 isotopologues were used to determine the precise semi-experimental equilibrium structure (r(e)(SE)) of thiazole. As a basis for comparison, a purely theoretical equilibrium structure was estimated by an electronic structure calculation [CCSD(T)/cc-pCV5Z] that was subsequently corrected for extrapolation to the complete basis set, electron correlation beyond CCSD(T), relativistic effects, and the diagonal Born–Oppenheimer correction. The precise r(e)(SE) structure is compared to the resulting “best theoretical estimate” structure. Some, but not all, of the best theoretical r(e) structural parameters fall within the narrow statistical limits (2σ) of the r(e)(SE) results. The possible origin of the discrepancies between the best theoretical estimate r(e) and semi-empirical r(e)(SE) structures is discussed.

The rotational spectrum of thiophene (c-C(4)H(4)S) has been collected between 8 and 360 GHz. Samples of varying deuterium-enrichment were synthesized to yield all possible deuterium-substituted isotopologues of thiophene. A total of 26 isotopologues have been measured and least-squares fit using A- and S-reduced distorted-rotor Hamiltonians in the I(r) representation. The resultant rotational constants (A(0), B(0), and C(0)) from each reduction were converted to determinable constants (A″, B″, and C″) to remove the impact of centrifugal distortion. The computed vibrational and electron mass corrections [CCSD(T)/cc-pCVTZ] were applied to the determinable constants to obtain semi-experimental equilibrium rotational constants (A(e), B(e), and C(e)) for 24 isotopologues. A precise semi-experimental equilibrium (r(e)(SE)) structure has been achieved from a least-squares fit of the equilibrium moments of inertia. The combination of the expanded isotopologue rotational data with high-level computational work establishes a precise r(e)(SE) structure for this sulfur-containing heterocycle. The CCSD(T)/cc-pCV5Z structure has been obtained and corrected for the extrapolation to the complete basis set, electron correlation beyond CCSD(T), relativistic effects, and the diagonal Born–Oppenheimer correction. The precise r(e)(SE) structure is compared to the resulting “best theoretical estimate” structure. Several of the best theoretical r(e) structural parameters fall within the narrow statistical limits (2σ) of the r(e)(SE) results. The possible origin of the discrepancies for the computed parameters that fall outside the statistical uncertainties is discussed.

OBJECTIVE: Parenting and parent-child relationships change dramatically during development. One unique feature of developmental changes in parenting–lability–is associated with adolescent problem behaviors, above and beyond the general level and developmental trends of parenting. This study investigated lability in parental warmth in childhood, its associations with early adolescent adjustment, as well as antecedents in kindergarten: socioeconomic status (SES), parental depressive symptoms, and child problem behaviors. METHOD: Using longitudinal data from a large and racially diverse sample (N = 710, 46% urban Black, 58% male), parents reported their warmth annually from kindergarten to grade 5, as well as child externalizing and internalizing problems in grade 7. Teachers rated child social competence in grade 6. RESULTS: Lability accounted for the majority of the variance in the year-to-year changes in parental warmth. Greater lability was associated with more internalizing problems and lower social competence. There was little evidence of the influence of child problem behaviors and parental depressive symptoms on lability. However, parents from lower-SES families showed greater lability in their warmth. Furthermore, lability partly explained the effects of SES on social competence in boys but not in girls, whereas the indirect effects of SES on internalizing problems through lability were significant in girls but not in boys. CONCLUSIONS: The findings highlight lability in parental warmth as a unique feature of the developmental changes in parenting in childhood, with linkages to adjustment in early adolescence. Family-based interventions should emphasize consistent parenting and provide stress management and coping skills for parents in order to reduce lability.

Even though risk assessment tools are often intended to inform case planning, they do not provide much direct guidance. As such, we developed an intervention-planning tool called the Adolescent Risk Reduction and Resilient Outcomes Work-Plan (ARROW) to accompany the Structured Assessment of Violence Risk in Youth. The ARROW includes a decision support system, guide, and training, and is one of the first tools of its kind. To evaluate the ARROW, we conducted two studies: (a) a vignette study with 178 professionals and (b) a field study with 320 propensity-score matched adolescents. Most professionals (>98%) rated the ARROW as useful. Moreover, compared with (a) unstructured plans and (b) a simple form, ARROW plans were more likely to include supported interventions, adhere to best practices, and integrate culturally tailored approaches for Indigenous adolescents. Formulations also showed improvements. However, further research is needed on strategies to bridge risk assessment and risk management.

Parental harsh punishment and warmth have been associated with child and adolescent conduct disorder (CD) symptoms and callous-unemotional (CU) traits (i.e., lack of guilt, empathy, and deficient affect); however, it is unclear whether the effect of these parenting behaviors on antisocial outcomes persists into adulthood. Thus, the present study aimed to test whether adolescent CD symptoms and CU traits mediate the effects of parental harsh punishment and warmth on adult antisocial outcomes (i.e., antisocial personality disorder (ASPD), externalizing psychopathology, partner violence, and violent and substance crime). Participants included the high-risk control and normative samples from the Fast Track project (N = 753, male = 58%, African American = 46%). Harsh punishment during kindergarten through grades 1-2 predicted higher adolescent CD symptoms, and directly observed warmth during kindergarten through grades 1-2 predicted lower adolescent CU traits. Adolescent CD symptoms predicted greater adult substance crime, and adolescent CU traits predicted greater adult ASPD symptoms and externalizing psychopathology. Further, adolescent CD symptoms indirectly accounted for the effect of parental harsh punishment on adult substance crime, and adolescent CU traits indirectly accounted for the effect of parental warmth on ASPD symptoms and externalizing psychopathology. Findings support the importance of early interventions targeting parenting behaviors to reduce risk for the development of antisocial behavior, and inform developmental models of antisocial behavior in adolescence through adulthood.

The 1 H- and 2 H-1,2,3-triazoles are isomeric five-membered ring, aromatic heterocycles that may undergo chemical equilibration by virtue of intramolecular hydrogen migration (tautomerization). Using millimeter-wave spectroscopy in the 130–375 GHz frequency range, we measured the spectroscopic constants for thirteen 1 H-1,2,3-triazole and sixteen 2 H-1,2,3-triazole isotopologues. Herein, we provide highly accurate and highly precise semi-experimental equilibrium ( r eSE) structures for the two tautomers based on the spectroscopic constants of each set of isotopologues, together with vibration–rotation interaction and electron-mass distribution corrections calculated using coupled-cluster singles, doubles, and perturbative triples calculations [CCSD(T)/cc-pCVTZ]. The resultant structures are compared with a “best theoretical estimate” (BTE), which has recently been shown to be in exceptional agreement with the semi-experimental equilibrium structures of other aromatic molecules. Bond distances of the 1 H tautomer are determined to eSE values is discussed.

Hydrazoic acid (HN3) is used as a case study for investigating the accuracy and precision by which a molecular structure—specifically, a semi-experimental equilibrium structure ( r eSE)—may be determined using current state-of-the-art methodology. The influence of the theoretical corrections for effects of vibration–rotation coupling and electron-mass distribution that are employed in the analysis is explored in detail. The small size of HN3 allowed us to deploy considerable computational resources to probe the basis-set dependence of these corrections using a series of coupled-cluster single, double, perturbative triple [CCSD(T)] calculations with cc-pCV XZ ( X = D, T, Q, 5) basis sets. We extrapolated the resulting corrections to the complete basis set (CBS) limit to obtain CCSD(T)/CBS corrections, which were used in a subsequent r eSE structure determination. The r eSE parameters obtained using the CCSD(T)/cc-pCV5Z corrections are nearly identical to those obtained using the CCSD(T)/CBS corrections, with uncertainties in the bond distances and angles of less than 0.0006 Å and 0.08°, respectively. The previously obtained r eSE structure using CCSD(T)/ANO2 agrees with that using CCSD(T)/cc-pCV5Z to within 0.000 08 Å and 0.016° for bond distances and angles, respectively, and with only 25% larger uncertainties, validating the idea that r eSE structure determinations can be carried out with significantly smaller basis sets than those needed for similarly accurate, strictly ab initio determinations. Although the purely computational r e structural parameters [CCSD(T)/cc-pCV6Z] fall outside of the statistical uncertainties (2σ) of the corresponding r eSE structural parameters, the discrepancy is rectified by applying corrections to address the theoretical limitations of the CCSD(T)/cc-pCV6Z geometry with respect to basis set, electron correlation, relativity, and the Born–Oppenheimer approximation, thereby supporting the contention that the semi-experimental approach is both an accurate and vastly more efficient method for structure determinations than is brute-force computation.